Certain cyano containing aryl amides, compositions containing same and fungicidal use thereof

ABSTRACT

Amide derivatives of the formula (I) ##STR1## wherein R 1  is phenyl optionally substituted with halogen, lower alkyl, lower alkoxy, halo-lower alkoxy, methylenedioxy, lower alkylthio or cyano; 
     R 2  is hydrogen, C 1  -C 4  alkyl or C 3  -C 5  alkenyl; 
     X is oxygen or sulfur 
     R 3  is lower alkyl, lower haloalkyl or lower alkenyl; and 
     E is --CN. 
     These amides possess fungicidal and herbicidal properties.

This invention relates to substituted benzamide derivatives useful asherbicides and fungicides, to processes of combatting weeds and fungalinfestations and to herbicidal and fungicidal compositions.

Substituted benzamide derivatives have previously been proposed for useas herbicides; by way of example, the compounds disclosed in U.K. patentspecification Nos. 1,209,608 and 1,395,802 may be mentioned.

According to the present invention, there are provided amide derivativesof the formula (I) ##STR2## wherein R¹ is an optionally substitutedalkyl, alkenyl, aryl, heterocyclyl, benzyl, or heterocyclylmethylradical;

R² is hydrogen, or an optionally substituted alkyl, alkenyl, benzyl, orheterocyclylmethyl, radical;

X is oxygen, sulphur, or an --NH-- group;

R³ is an optionally substituted alkyl or alkenyl radical when X isoxygen or sulphur, or is an optionally substituted alkanoyl radical whenX is --NH--;

and E is a --CN, --CONH₂, --CSNH₂, or --CONR⁴ R⁵ group wherein each R⁴and R⁵ is hydrogen or an optionally substituted alkyl or alkenyl group.

When the group R¹ is an optionally substituted alkyl or alkenyl radical,it may be for example C₁₋₅ alkyl or C₃₋₅ alkenyl radical. Examples ofsubstituents include C₁ -C₄ alkoxy, C₁ -C₄ alkylthio and halogen (i.e.fluorine, chlorine, bromine or iodine).

When R¹ is a benzyl radical optionally substituted in the phenyl ring,examples of substituents include halogen (fluorine, chlorine, bromine oriodine), C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, nitro, cyano, C₁ -C₄ haloalkyl(e.g. CF₃), and C₁ -C₄ alkyl (e.g. CH₃). There may be from one to fivesubstituents, which may be the same or different.

When R¹ is an optionally substituted aryl group it may be a phenyl ornaphthyl radical. Examples of substituents which may be present includefluorine, chlorine, bromine, iodine, C₁ -C₄ alkoxy, methylenedioxy andethylenedioxy, C₁ -C₄ alkyl, C₁ -C₄ alkylthio, C₁ -C₄ haloalkyl (e.g.CF₃) nitro and cyano. There may be from one to three or moresubstituents which may be the same or different. When R¹ is asubstituted phenyl radical the substituents are preferably in the 3, 4,or 5 positions. When a methylenedioxy or ethylenedioxy substituent ispresent, it preferably is attached to the 3 and 4 positions of thephenyl ring. A halogen substituent (e.g. Cl or Br) may also be presentin the 4- or 5-position, or both, in such compounds.

When R¹ is an optionally substituted heterocyclyl radical, it may forexample be a furyl, benzfuryl, thienyl, pyridyl, thiazolyl, orbenzthiazolyl radical. Examples of substituents which may be presentinclude those listed above for the case when R¹ is a substituted phenylradical. There may be from one to three or more substituents which maybe the same or different.

When R¹ is an optionally substituted heterocyclylmethyl radical, theheterocyclyl group may be for example a furyl, thienyl, pyridyl,thiazolyl or benzthiazolyl group. Examples of substituents which may bepresent in the heterocyclyl group include those described above for thecase when R¹ is a substituted phenyl radical.

R² is preferably hydrogen but when it is not, then it may be anoptionally substituted alkyl group, for example an C₁ -C₄ alkyl group.Examples of substituents which may be present include fluorine,chlorine, bromine, iodine, and C₁ -C₄ alkoxy. When R² is an optionallysubstituted alkenyl group it may be for example an alkenyl group of from3-5 carbon atoms. Examples of substituents which may be present includethose listed above for the case when R² is an alkyl group.

When R² is an optionally substituted benzyl group, the substituents mayinclude those described above for the case when R¹ is substitutedbenzyl.

When R² is an optionally substituted heterocyclylmethyl group, theheterocyclyl ring may be for example a furyl, thienyl, pyridyl,thiazolyl, or benzothiazolyl ring. Substituents which may be presentinclude those described above for the case where R¹ is a substitutedphenyl radical.

When R³ is an optionally substituted alkyl or alkenyl radical it mayhave any of the values described above for the group R².

When R³ is an alkanoyl group (i.e. when X is NH) it may for example havefrom 1 to 4 carbon atoms (e.g. it may be a formyl, acetyl, or propionylgroup).

R⁴ and R⁵ are preferably hydrogen, but when they are not, they may beoptionally substituted alkyl or alkenyl group it may have any of thevalues defined above for the group R² when it is an optionallysubstituted alkyl or alkenyl radical.

Within the above definition, one sub-class of compounds according to theinvention comprises those compounds wherein R² is hydrogen. Within thissub-class, a further sub-class comprises those compounds in which E is acyano group, X is O or S, and R³ is C₁ -C₄ alkyl A group within thelatter sub-class includes those compounds in which R¹ is phenyl orheterocyclyl. Within the latter group, a sub-group includes compounds inwhich the heterocyclyl or phenyl group is substituted, for example byalkyl, alkoxy, methylenedioxy, or halogen, for example fluorine orchlorine. In such compounds the groups or atoms are preferably locatedin the 3, 4 or 5 positions of the phenyl ring.

The structural formula (I) given above is believed to be the one whichbest represents the structure of the compounds. For some compoundswithin the scope of the formula (I) it may be possible in principle fortautomeric forms of the compound to exist, in which a hydrogen atom istransposed to another part of the molecule and the chemical bondsbetween the atoms of the molecule are consequently rearranged; thus,where R¹ is hydrogen, it is possible in principle for the molecule toexist in the alternative form (II) ##STR3##

The structural formula (I) is intended to represent and include suchtautomeric forms, insofar as they may exist. The structural formula (I)is also intended to include any physically distinguishable modificationsof the compounds which may arise, for example, from different ways inwhich the molecules are arranged in a crystal lattice, or from theinability of parts of the molecules to rotate freely in relation toother parts, or from geometrical and or optical isomerism, or fromintramolecular or inter-molecular bonding, or otherwise.

Particular examples of compounds according to the invention are listedin Table I below:

                                      TABLE 1                                     __________________________________________________________________________     ##STR4##                                                                     COMPOUND                                           Melting                                                                            Notes (see            NO      R.sup.1    R.sup.2   XR.sup.3 E        Route                                                                             Point                                                                              end of                __________________________________________________________________________                                                            Table)                1       C.sub.6 H.sub.5                                                                          H         OMe      CONHMe   A   155                        2       C.sub.6 H.sub.5                                                                          H         OMe      CN       A    83                        3       C.sub.6 H.sub.5                                                                          H         OEt      CONH.sub.2                                                                             A   148-150                    4       C.sub.6 H.sub.5                                                                          H         OEt      CN       A   107-110                    5       C.sub.6 H.sub.5                                                                          H         OPr.sup.n                                                                              CONH.sub.2                                                                             A   105-108                    6       C.sub.6 H.sub.5                                                                          H         OPr.sup.i                                                                              CONH.sub.2                                                                             A   119-121                    7       C.sub.6 H.sub.5                                                                          H         OBu.sup.n                                                                              CONH.sub.2                                                                             A   85-88                      8       C.sub.6 H.sub.5                                                                          H         OPr.sup.i                                                                              CN       A   118-119                    9       C.sub.6 H.sub.5                                                                          H         OBu.sup.n                                                                              CN       A   74-77                      10      C.sub.6 H.sub.5                                                                          H         OBu.sup.t                                                                              CONH.sub.2                                                                             A   150-154                    11      C.sub.6 H.sub.5                                                                          H         OBu.sup.s                                                                              CONH.sub.2                                                                             A   94-95                      12      C.sub.6 H.sub.5                                                                          H         OBu.sup.t                                                                              CN       A   117-120                    13      C.sub.6 H.sub.5                                                                          H         OBu.sup.s                                                                              CN       A   77-79                      14      4-Cl.C.sub.6 H.sub.4.                                                                    H         OMe      CONH.sub.2                                                                             A   164-166                    15      4-Cl.C.sub.6 H.sub.4.                                                                    H         OMe      CN       A   123-125                    16      2-Cl.C.sub.6 H.sub.4.                                                                    H         OMe      CONH.sub.2                                                                             A   110-112                    17      2-Cl.C.sub.6 H.sub.4.                                                                    H         OMe      CN       A   86-89                      18      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OMe      CN       A   155-158                    19      3-Cl.C.sub.6 H.sub.4.                                                                    H         OMe      CONH.sub.2                                                                             A   135-137                    20      3-Cl.C.sub.6 H.sub.4.                                                                    H         OMe      CN       A   90-92                      21      3,5(Me).sub.2.C.sub.6 H.sub.3.                                                           H         OMe      CONH.sub.2                                                                             A   171-173                    22      3,5(Me).sub.2.C.sub.6 H.sub.3.                                                           H         OMe      CN       A   107-108                    23      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OMe      CONH.sub.2                                                                             A   190-192                    24      C.sub.6 H.sub.5                                                                          H         OPr.sup.n                                                                              CN       A   91-93                      25      3-CF.sub.3.C.sub.6 H.sub.4.                                                              H         OEt      CONH.sub.2                                                                             A   151-153                    26      3-CF.sub.3.C.sub.6 H.sub.4.                                                              H         OEt      CN       A   54-56                      27      3-NO.sub. 2.C.sub.6 H.sub.4.                                                             H         OEt      CONH.sub.2                                                                             A   150-152                    28      3-NO.sub.2.C.sub.6 H.sub.4.                                                              H         OEt      CN       A    99-100                    29      3-Me.C.sub.6 H.sub.4.                                                                    H         OEt      CONH.sub.2                                                                             A   123-125                    30      3-Me.C.sub.6 H.sub.4.                                                                    H         OEt      CN       A   76-77                      31      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CONH.sub.2                                                                             A   188-189                    32      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OPr.sup.i                                                                              CONH.sub.2                                                                             A   178-180                    33      3,4-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CN       A   96-97                      34      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CN       A   156                        35      3-Br.C.sub.6 H.sub.4.                                                                    H         OEt      CONH.sub.2                                                                             A   152-153                    36      3-Br.C.sub.6 H.sub.4.                                                                    H         OEt      CN       A   93-95                      37      3-MeO.C.sub.6 H.sub.4.                                                                   H         OEt      CONH.sub.2                                                                             B   143-144                    38      3-MeO.C.sub.6 H.sub.4.                                                                   H         OEt      CN       B    72                        39      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OPr.sup.i                                                                              CN       A   128-130                    40      3-Cl.C.sub.6 H.sub.4.                                                                    H         SMe      CN       A   115-117                    41      3-Cl.C.sub.6 H.sub.4.                                                                    H         OEt      CN       A   90-91                      42      3,5-(CF.sub.3).sub.2.C.sub.6 H.sub.3.                                                    H         OEt      CN       A   114-116                    43      3-Cl.C.sub.6 H.sub.4.                                                                    H         OPr.sup.i                                                                              CN       A   82-84                      44      3-Cl.C.sub.6 H.sub.4.                                                                    H         OEt      CSNH.sub.2                                                                             G   136-137                    45      2,5-Cl.sub.2.C.sub.6 H.sub.4.                                                            H         OEt      CN       A   123-124                    46      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OCH.sub.2 CF.sub.3                                                                     CONH.sub.2                                                                             A   204-205                    47      3,4-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CSNH.sub.2                                                                             G   140                        48      3-F.C.sub.6 H.sub.4.                                                                     H         OEt      CONH.sub.2                                                                             A   112-113                    49      3-F.C.sub.6 H.sub.4.                                                                     H         OMe      CONH.sub.2                                                                             A   137-139                    50      2,6-(Me).sub.2.C.sub.6 H.sub.3.                                                          H         OMe      CN       B   65-67                      51      3-F.C.sub.6 H.sub.4.                                                                     H         OEt      CN       A   68-69                      52      3-F.C.sub.6 H.sub.4.                                                                     H         OMe      CN       A   86-88                      53      C.sub.6 H.sub.5                                                                          Me        OMe      CN       F   Oil  a                     54      3-Cl.C.sub.6 H.sub.4.                                                                    Me        OEt      CN       F   Oil  b                     55      3-Cl.C.sub.6 H.sub.4.                                                                    Me        OMe      CN       F   55-56                      56      3-Cl.C.sub.6 H.sub.4.                                                                    H         OEt      CONH.sub.2                                                                             A   134-136                    57      3,5(CF.sub.3).sub.2.C.sub.6 H.sub.3.                                                     H         OEt      CONH.sub.2                                                                             A   204-206                    58      3-Cl.C.sub.6 H.sub.4.                                                                    H         OPr.sup.i                                                                              CONH.sub.2                                                                             A   140-143                    59      2,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CONH.sub.2                                                                             A   163-165                    60      3-F.C.sub.6 H.sub.4.                                                                     H         OPr.sup.i                                                                              CONH.sub.2                                                                             A   140                        61      3-F.C.sub.6 H.sub.4.                                                                     H         OPr.sup.i                                                                              CN       A   82-83                      62      3-Me.C.sub.6 H.sub.4.                                                                    H         OMe      CN       B   68-71                      63      3-Me.C.sub.6 H.sub.4.                                                                    H         OPr.sup.i                                                                              CN       B   86-87                      64      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            Me        OMe      CN       F   88-90                      65      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            Me        OEt      CN       F   46-48                      66      3,5(Me).sub.2.C.sub.6 H.sub.3.                                                           H         OEt      CN       B   85-87                      67      F.sub.5.C.sub.6.                                                                         H         OEt      CN       A   85-86                      68      3-Me4-NO.sub.2.C.sub.6 H.sub.3.                                                          H         OEt      CONH.sub.2                                                                             A   116-118                    69      4-MeO3,5-Cl.sub.2.C.sub.6 H.sub.2.                                                       H         OEt      CN       B   119-122                    70      3-Me.C.sub.6 H.sub.4.                                                                    H         OMe      CSNH.sub.2                                                                             G   130-131                    71      3,5-(Me).sub.2.C.sub.6 H.sub.3.                                                          H         OEt      CSNH.sub.2                                                                             G   170-171                    72      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            Pr.sup.i  OMe      CN       F   79-81                      73      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            Et        OMe      CN       F   97-98                      74      3-Cl.C.sub.6 H.sub.4.                                                                    Et        OMe      CN       F   Oil  c                     75      3-Cl.C.sub.6 H.sub.4.                                                                    Pr.sup.i  OMe      CN       F   Oil  d                     76      3-Me.C.sub.6 H.sub.4.                                                                    Pr.sup.i  OMe      CN       F   Oil  e                     77      3-Me.C.sub.6 H.sub.4.                                                                    Et        OMe      CN       F   Oil  f                     78      3-Me.C.sub.6 H.sub.4.                                                                    Me        OMe      CN       F   Oil  g                     79      3,5(Me).sub.2.C.sub.6 H.sub.3.                                                           H         OEt      CONH.sub.2                                                                             B   180-183                    80      3-CN.C.sub.6 H.sub.4.                                                                    H         OEt      CONH.sub.2                                                                             A   157-158                    81      3-CN.C.sub.6 H.sub.4.                                                                    H         OEt      CN       A   112-115                    82      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OPr.sup.n                                                                              CONH.sub.2                                                                             A   178-180                    83      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OPr.sup.n                                                                              CN       A   137-138                    84      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OPr.sup.n                                                                              CSNH.sub.2                                                                             G   137-138                    85      2-naphthyl H         OEt      CN       A   117-118                    86      3-Cl5-NO.sub.2 .C.sub.6 H.sub.3.                                                         H         OEt      CN       A   133-136                    87      3-chlorobenzyl                                                                           H         OEt      CN       B   87-89                      88      2,6-dichloro-                                                                            H         OMe      CONH.sub.2                                                                             B   190-192                            4-pyridyl-                                                            89      3-Cl.C.sub.6 H.sub.4.                                                                    H         OCH.sub.2 CHCH.sub.2                                                                   CONH.sub.2                                                                             A   91-92                      90      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OCH.sub.2 CHCH.sub.2                                                                   CONH.sub.2                                                                             A   164-165                    91      3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OCH.sub.2 CHCH.sub.2                                                                   CN       A   134-135                    92      3-Cl.C.sub.6 H.sub.4.                                                                    H         OCH.sub.2 CHCH.sub.2                                                                   CN       A   64-66                      93      3-Cl.C.sub.6 H.sub.4.                                                                    H         SMe      CONH.sub.2                                                                             A   154-156                    94      3-Br.C.sub.6 H.sub.4.                                                                    H         OMe      CONH.sub.2                                                                             A   141-143                    95      3-Br.C.sub.6 H.sub.4.                                                                    H         OMe      CN       A   88-90                      96      3-Et.C.sub.6 H.sub.4.                                                                    H         OEt      CN       B   55-56                      97      3-Cl5-Me.C.sub.6 H.sub.3.                                                                H         OEt      CN       B   114-116                    98      3-Cl5-Me.C.sub.6 H.sub.3.                                                                H         OMe      CN       B    99-102                    99      2-furyl    H         OMe      CONH.sub.2                                                                             B   113-114                    100     2-furyl    H         OEt      CONH.sub.2                                                                             B   113-114                    101     2-furyl    H         OMe      CN       B   75-77                      102     2-furyl    H         OEt      CN       B   73-74                      103     2,6-dichloro-                                                                            H         OMe      CN       B   134-136                            4-pyridyl-                                                            104     2-benzthiazolyl                                                                          H         OMe      CN       B   116-118                    105     iso-pentyl H         OMe      CONH.sub.2                                                                             B    98-101                    106     iso-pentyl H         OMe      CN       B   Oil                        107     tert-C.sub.4 H.sub.9                                                                     H         OMe      CONH.sub.2                                                                             B   86-88                      108     tert-C.sub.4 H.sub.9                                                                     H         OMe      CN       B   59-60                      109     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         SMe      CN       A   150-152                    110     3-Me.C.sub.6 H.sub.4.                                                                    H         SMe      CN       B   119-120                    111     3-Br.C.sub.6 H.sub.4.                                                                    H         OEt      CSNH.sub.2                                                                             G   145-146                    112     2-naphthyl H         OMe      CN       A   117-118                    113     3-MeO.C.sub.6 H.sub.4.                                                                   H         OMe      CONH.sub.2                                                                             B   106-108                    114     3-Cl5-NO.sub.2.C.sub.6 H.sub.3.                                                          H         OEt      CONH.sub.2                                                                             A   190-192                    115     5-Cl2-MeO.C.sub.6 H.sub.3.                                                               H         OEt      CONH.sub.2                                                                             B   177-180                    116     5-Cl2-MeO.C.sub.6 H.sub.3.                                                               H         OEt      CN       B   109-112                    117     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OCH.sub.2 CF.sub.3                                                                     CN       A   148-149                    118     3-MeO.C.sub.6 H.sub.4.                                                                   H         OMe      CN       B   80- 81                     119     3,5(MeO).sub.2.C.sub.6 H.sub.3.                                                          H         OMe      CN       B    98-100                    120     3,5(MeO).sub.2.C.sub.6 H.sub.3.                                                          H         OEt      CN       B   86-88                      121     C.sub.6 H.sub.5 CH.sub.2.                                                                H         OMe      CN       B   67-68                      122     3-F.C.sub.6 H.sub.4.                                                                     Me        OMe      CN       F   Oil  h                     123     3-I.C.sub.6 H.sub.4.                                                                     H         OEt      CONH.sub.2                                                                             A   174-176                    124     3-I.C.sub.6 H.sub.4.                                                                     H         OMe      CONH.sub.2                                                                             A   147-148                    125     3-I.C.sub.6 H.sub.4.                                                                     H         OEt      CN       A   123-125                    126     3-I.C.sub.6 H.sub.4.                                                                     H         OMe      CN       A    98-101                    127     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            CH.sub.2 Ph                                                                             OMe      CN       F   59-61                      128     3-Cl.C.sub.6 H.sub.4.                                                                    CH.sub.2 Ph                                                                             OMe      CN       F   Oil  i                     129     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CONHMe   B   184-185                    130     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CONMe.sub.2                                                                            B   90-92                      131     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OEt                                                                                     ##STR5##                                                                              B   112-113                    132     3-Cl5-Me.C.sub.6 H.sub.3.                                                                H         OEt      CONH.sub.2                                                                             B   169-171                    133     3,5-F.sub.2.C.sub.6 H.sub.3.                                                             H         OEt      CONH.sub.2                                                                             A   173-175                    134     3,5-F.sub.2.C.sub.6 H.sub.3.                                                             H         OEt      CN       A   111-112                    135     3-Cl4,5-F.sub.2.C.sub.6 H.sub.2.                                                         H         OEt      CONH.sub.2                                                                             A   167-168                    136     3-Cl4,5-F.sub.2.C.sub.6 H.sub.2.                                                         H         OEt      CN       A   146-149                    137     C.sub.6 H.sub.5.                                                                         H         NHAc     CONH.sub.2                                                                             D   243-245                    138     C.sub.6 H.sub.5.                                                                         H         NHAc     CN       D   193-194                    139     C.sub.6 H.sub.5.                                                                         H         NHAc     CONHMe   D   207-209                    140     3,5-Br.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CONH.sub.2                                                                             A   203-205                    141     3,5-Br.sub.2.C.sub.6 H.sub.3.                                                            H         OEt      CN       A   165-167                    142     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            CH.sub.2 Ph                                                                             OEt      CN       F   Oil  j                     143     3-Eto.C.sub.6 H.sub.4.                                                                   H         OEt      CONH.sub.2                                                                             B                              144     3-Eto.C.sub.6 H.sub.4.                                                                   H         OEt      CN       B   95-97                      145     3,4,5-Cl.sub.3.C.sub.6 H.sub.2.                                                          H         OEt      CONH.sub.2                                                                             A   203-204                    146     3,4,5-Cl.sub.3.C.sub.6 H.sub.2.                                                          H         OEt      CN       A   139-141                    147     3,5-Cl.sub.2.C.sub. 6 H.sub.3.                                                           H         OCH.sub.2 CH.sub.2 CH.sub.2 Cl                                                         CONH.sub.2                                                                             A   169-172                    148     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         OCH.sub.2 CH.sub.2 CH.sub.2 Cl                                                         CN       A   123-124                    149     3-F.C.sub.6 H.sub.4.                                                                     H         NHAc     CONH.sub.2                                                                             D   238-240                    150     C.sub.6 H.sub.5.                                                                         CH.sub.2 Ph                                                                             OMe      CN       F   Oil                        151     3-F.C.sub.6 H.sub.4.                                                                     CH.sub.2 Ph                                                                             OMe      CN       F   Oil  k                     152     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         NHAc     CONH.sub.2                                                                             D   267-268                    153     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            H         NHAc     CN       D   227-228                    154     3,5-Me.sub.2.C.sub.6 H.sub.3.                                                            H         NHAc     CONH.sub.2                                                                             C   244-245                    155     3-F.C.sub.6 H.sub.4.                                                                     H         NHAc     CN       D   175-176                    156     3,5-Me.sub.2.C.sub.6 H.sub.3.                                                            CH.sub.2 Ph                                                                             OMe      CN       F   Oil  k                     157     3-Me.C.sub.6 H.sub.4.                                                                    CH.sub.2 Ph                                                                             OMe      CN       F   Oil  l                     158     3,5-Me.sub.2.C.sub.6 H.sub.3.                                                            H         NHAc     CN       C   195-197                    159     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                             ##STR6## OMe      CN       E   89-90                      160     3,5-F.sub.2.C.sub.6 H.sub.3.                                                             CH.sub.2 Ph                                                                             OMe      CN       F   Oil  m                     161     3-Cl.C.sub.6 H.sub.4.                                                                     ##STR7## OMe      CN       E   48-49                      162     3,5-Me.sub.2.C.sub.6 H.sub.3.                                                            H         NHCOCHCH.sub.2                                                                         CONH.sub.2                                                                             C   201-203                    163     3,5-Me.sub.2.C.sub.6 H.sub.3.                                                            H         NHCOCHCH.sub.2                                                                         CN       C   191-193                    164     3,5-Cl.sub.2 C.sub.6 H.sub.3.                                                            H         NHCOCHCH.sub.2                                                                         CONH.sub.2                                                                             C   223-225                    165     3,5-Cl.sub.2 C.sub.6 H.sub.3.                                                            H         NHCOCHCH.sub.2                                                                         CN       C   220-222                    166     3,4,5-F.sub.3 C.sub.6 H.sub.2.                                                           H         OEt      CONH.sub.2                                                                             A   155-156                    167     3,4,5-F.sub.3 C.sub.6 H.sub.2.                                                           H         OEt      CN       A   129-131                    168     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            Allyl     OMe      CONH.sub.2                                                                             E   176-178                    169     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            Allyl     OMe      CN       E   Oil                        170     3,5-Cl.sub.2.C.sub.6 H.sub.3.                                                            C.sub.6 H.sub.5                                                                         OMe      CN       E   Oil                        171     3,5-F.sub.2 C.sub.6 H.sub.3                                                              H         NHAC     CONH.sub.2                                                                             C   197-200                    172     3,4-OCH.sub.2 O.C.sub.6 H.sub.3                                                          H         OEt      CONH.sub.2                                                                             B   159-161                    173     3,4,5-F.sub.3 C.sub.6 H.sub.2                                                            H         OCH.sub.2 CHCH.sub.2                                                                   CONH.sub.2                                                                             A   104-106                    174     3,4,5-F.sub.3 C.sub.6 H.sub.2                                                            H         OCH.sub.2 CHCH.sub.2                                                                   CN       A   109-111                    175     3,4-OCH.sub.2 OC.sub.6 H.sub.3                                                           H         OEt      CN       B   155-156                    176     3-ClC.sub.6 H.sub.4                                                                      Allyl     OMe      CONH.sub.2                                                                             E   115-116                    177     3-ClC.sub.6 H.sub.4                                                                      CH.sub.2 CHCH.sub.2                                                                     OMe      CN       E   Oil                        178     2-HOC.sub.6 H.sub.4                                                                      H         OEt      CN       B   Oil                        179     2-ACOC.sub.6 H.sub.4                                                                     H         OEt      CN       B   83-87                      180     3-FC.sub.6 H.sub.4                                                                       H         OCH.sub.2 CF.sub.3                                                                     CONH.sub.2                                                                             A   104-106                    181     3-FC.sub.6 H.sub.4                                                                       H         OCH.sub.2 CF.sub.3                                                                     CN       A   106-107                    182     3,4,5-F.sub.3 C.sub.6 H.sub.2                                                            H         NHAC     CONH.sub.2                                                                             C   241-242                    183     3,4,5-F.sub.3 C.sub.6 H.sub.2                                                            H         NHAC     CN       C   210-211                    184     3,5-Cl.sub.2 C.sub.6 H.sub.3                                                             H         OCH.sub.2 CH.sub.2 Br                                                                  CONH.sub.2                                                                             A   165-166                    185     3,5-F.sub.2 C.sub.6 H.sub.3                                                              H         OCH.sub.2 CH.sub.2 Br                                                                  CONH.sub.2                                                                             A   160-162                    186     3,5-F.sub. 2 C.sub.6 H.sub.3                                                             H         NHAC     CN       C   204-206                    187     3-FC.sub.6 H.sub.4                                                                       H                                                                                        ##STR8##                                                                              CN       C   185-187                    188     3,5-Cl.sub.2 C.sub.6 H.sub.3                                                             H         OCH.sub.2 CH.sub.2 Cl                                                                  CONH.sub.2                                                                             A   176-178                    189     4-MeOC.sub.6 H.sub.4                                                                     H         OEt      CONH.sub.2                                                                             B   169-170                    190     4-MeOC.sub.6 H.sub.4                                                                     H         OEt      CN       B   87-89                      191     3,4-OCH.sub.2 OC.sub.6 H.sub.3                                                           H         SMe      CONH.sub.2                                                                             B   185-187                    192     3,4-OCH.sub.2 OC.sub.6 H.sub.3                                                           H         SMe      CN       B   139-141                    193                                                                                    ##STR9##  H         OMe      CONH.sub.2                                                                             B   214-215                    194                                                                                    ##STR10## H         OMe      CN       B   110-111                    195     3-ClC.sub.6 H.sub.4                                                                      Me        SMe      CN       F   Oil                        196     4-MeC.sub.6 H.sub.4                                                                      H         OEt      CN       B   133-135                    197     4-ClC.sub.6 H.sub.4                                                                      H         OEt      CN       A   102-103                    198     3,4-Me.sub.2 C.sub.6 H.sub.3                                                             H         OEt      CN       A   94-96                      199     4-BrC.sub.6 H.sub.4                                                                      H         OEt      CN       A   113-114                    200     4-CNC.sub. 6 H.sub.4                                                                     H         OEt      CN       A   103-104                    201     3,4(MeO).sub.2 C.sub.6 H.sub.3                                                           H         OEt      CN       B   121-123                    202     3-Cl4-HOC.sub.6 H.sub.3                                                                  H         OEt      CN       B   90-92                      203     3-Cl4-ACOC.sub.6 H.sub.3                                                                 H         OEt      CN       B   126-128                    204     3-Cl4-MeC.sub.6 H.sub.3                                                                  H         OEt      CN       A   113-114                    205     3,5-Cl.sub.24-MeC.sub.6 H.sub.2                                                          H         OEt      CN       A                              206     4-CF.sub.3 C.sub.6 H.sub.4                                                               H         OEt      CN       A   114-115                    207     3-Cl4-OMeC.sub.6 H.sub.3                                                                 H         OEt      CN       B                              208     3-Br4-OMeC.sub.6 H.sub.3                                                                 H         OEt      CN       B                              209     3,4,5-Me.sub.3 C.sub.6 H.sub.2                                                           H         OEt      CN       B                              210     4-EtC.sub.6 H.sub.4                                                                      H         OEt      CN       A   115-116                    __________________________________________________________________________    NOTES                                                                         The abbreviations used in Table I are standard chemical                       symbols. Thus the symbols Me, Et, Pr and Ph stand for                         methyl, ethyl, propyl, and phenyl groups respectively, and                    the symbols F.sub.5.C.sub.6. and 3-Cl5-NO.sub.2.C.sub.6 H.sub.3., for         example, stand for pentafluorophenyl and 3-chloro-5-nitro-                    phenyl respectively.                                                          Melting points are given for most compounds in the table.                     Where the compound is an oil, a refractive index                              measurement or nuclear magnetic resonance (NMR) data are                      given in the notes below. In the NMR information, the                         symbols have the following meanings:-                                         s singlet                                                                     t triplet                                                                     q quartet                                                                     m multiplet                                                                   d doublet                                                                     Chemical shifts (δ) are quoted relative to tetramethyl-                 silane. The solvent used was deuterochloroform.                               Notes for individual compounds follow:-                                       a Refractive index n.sub.D.sup.21 = 1.5233                                    b Refractive index n.sub.D.sup.21 = 1.5197                                    c NMR data: δ = 1.3 (3H,t), 3.45 (3H,s), 3.7 (2H,q),                    5.95 (H,S,broad), ca 7.5 (4H,m)                                               d NMR data: δ = 1.5 (6H,d), 2.35 (3H,s), 3.3 (3H,s),                    4.1 (1H,m), 5.5 (1H,s), ca. 7.2 (4H,m).                                       e NMR data: δ = 1.5 (6H,d), 2.35 (3H,s), 3.3 (3H,s),                    4.1 (1H,m), 5.5 (1H,s), ca. 7.2 (4H,m)                                        f NMR data: δ = 1.3 (3H,t), 2.4 (3H,s), 3.7 (2H,q),                     5.95 (1H,s,broad), ca. 7.3 (4H,m)                                             g NMR data: δ = 2.4 (3H,s), 3.1 (3H,s), 3.4 (3H,s),                     ca. 6.1 (1H,s,very broad), ca. 7.3 (4H,m)                                     h NMR data: δ = 3.1 (3H,s), 3.4 (3H,s), 6.1 (s,very broad),             ca. 7.2 (4H,m).                                                               i NMR data: δ = 3.4 (3H,s), 4.75 (2H,s), 5.9 (1H,s),                    ca. 7.3 (9H,m).                                                               j NMR data: δ = 1.2 (3H,t), 3.55 (2H,q), 4.7 (2H,d),                    5.95 (1H,broad), ca. 7.2 (8H,m).                                              k NMR data: δ = 3.35 (3H,s), 4.75 (2H,s), 5.9 (1H,s,broad),             ca. 7.2 (9H,m)                                                                l NMR data: δ = 2.3 (6H,s), 3.3 (3H,s), 4.75 (2H,s)                     5.9 (1H,s,broad), 7.0-7.4 (8H,m).                                             m NMR data: δ = 3.4 (3H,s), 4.75 (2H,s), 5.9 (1H,s,broad),              ca. 6.8-7.3 (8H,m)                                                        

In another aspect the invention provides a process of inhibiting thegrowth of unwanted plants, which comprises applying to the plants, or tothe locus thereof, a phytotoxic amount of a compound of the formula (I)as hereinbefore defined. The amount of the compound may vary, dependingupon the identity of the particular compound chosen and the plantspecies whose growth is to be inhibited, but in general amounts of from0.01 to 5.0 kilograms per hectare will be suitable; usually the amountwill be from 0.2 to 1.0 kilograms per hectare. The skilled worker in theherbicide art will readily be able to establish appropriate applicationrates by standard procedures without undue experimentation.

The compounds of the invention are relatively less toxic towards certaincrop plants than they are towards other plant species; accordingly,there is the possibility of using the compounds for selective weedcontrol in these crops. Examples of such crops include cotton, sugarbeet, rape, lettuce, peas; the compounds may be useful in a number ofcrops of the families Compositae and Leguminosae.

The compounds used in the process of the invention are preferablyapplied in the form of a composition, in which the active ingredient ismixed with a carrier comprising a solid or liquid diluent. In anotheraspect, therefore, the invention provides a herbicidal composition,comprising as an active ingredient a compound of the formula (I) ashereinbefore defined, in admixture with a solid or liquid diluent.Preferably the composition also comprises a surface-active agent.

The solid compositions of the invention may be for example, in the formof dusting powders, or may take the form of granules. Suitable soliddiluents include, for example, kaolin, bentonite, kieselguhr, dolomite,calcium carbonate, talc, powdered magnesia, and Fuller's Earth.

Solid compositions may also be in the form of dispersible powders orgrains comprising in addition to the active ingredient, a wetting agentto facilitate the dispersion of the powder or grains in liquids. Suchpowders or grains may include fillers, suspending agents and the like.

Liquid compositions include aqueous solutions, dispersions and emulsionscontaining the active ingredient preferably in the presence of one ormore surface active agents. Water or organic liquids may be used toprepare solutions, dispersions, or emulsions of the active ingredient.The liquid compositions of the invention may also contain one or morecorrosion inhibitors for example lauryl isoquinolinium bromide.

Surface active agents may be of the cationic, anionic or non-ionic type.Suitable agents of the cationic type include for example quaternaryammonium compounds, for example cetyltrimethyl ammonium bromide.Suitable agents of the anionic type include for example soaps, salts ofaliphatic mono-esters of sulphuric acid, for example sodium laurylsulphate; and salts of sulphonated aromatic compounds, for exampledodecylbenzenesulphonate, sodium, calcium and ammonium lignosulphonate,butylnaphthalene sulphonate, and a mixture of the sodium salts ofdiisopropyl- and triisopropyl-naphthalenesulphonic acid. Suitable agentsof the non-ionic type include, for example, the condensation products ofethylene oxide with fatty alcohols such as oleyl alcohol and cetylalcohol, or with alkyl phenols such as octyl-phenol, nonylphenol, andoctylcresol. Other non-ionic agents are the partial esters derived fromlong chain fatty acids and hexitol anhydrides, for example sorbitolmonolaurate; the condensation products of the said partial esters withethylene oxide and the lecithins.

The compositions which are to be used in the form of aqueous solution,dispersions or emulsions are generally supplied in the form of aconcentrate containing a high proportion of the active ingredient, theconcentrate being diluted with water before use. These concentrates areusually required to withstand storage for prolonged periods and aftersuch storage to be capable of dilution with water in order to formaqueous preparations which remain homogenous for a sufficient time toenble them to be applied by conventional spray equipment.

The compositions of the invention may contain, in addition to carriersand surface-active agents, various other constituents to increase theirusefulness. They may contain, for example, buffering salts to maintainthe pH of the composition within a desired range; antifreeze agents, forexample urea or propylene glycol; adjuvants, for example oils andhumectants; and sequestrants, for example citric acid andethylenediaminetetracetic acid, which help to prevent the formation ofinsoluble precipitates when the compositions are diluted with hardwater. Aqueous dispersions may contain anti-settling agents andanti-caking agents. The compositions may in general contain a dye orpigment to impart a characteristic colour. Agents for increasingviscosity may be added to reduce the formation of fine droplets duringspraying, and thereby reduce spray drift. Other additives useful forparticular purposes will be known to those skilled in the formulationart.

In general concentrates may conveniently contain from 10 to 85% andpreferably from 25 to 60% by weight of active ingredient. Dilutepreparations ready for use may contain varying amounts of the activeingredient, depending upon the purpose for which they are to be used;however, dilute preparations suitable for many uses contain between0.01% and 10% and preferably between 0.1% and 1% by weight of the activeingredient.

The invention further provides processes for preparing compounds offormula (I) above. Thus, compounds wherein R² is hydrogen may beprepared, for example, by the process of Scheme A below: ##STR11##

The process outlined in Scheme A begins with step (a), in which an acidchloride R¹ COCl is reacted with aminoacetonitrile by a conventionalprocedure to obtain the acylaminoacetonitrile derivative (III). This isthen reacted in step (b) with a brominating agent (for example brominein glacial acetic acid) to give the brominated derivative (IV). Thisbromination procedure also simultaneously hydrates the cyano group to acarbamoyl group --CONH₂, and necessitates treatment with a dehydratingagent at a later stage to convert the carbamoyl group back into a cyanogroup. It may be possible to avoid the undesired conversion of the cyanogroup to carbamoyl by use of a different solvent or brominating agentand thereby shorten the process by making step (d) unnecessary.

In step (c), the bromo compound (IV) is reacted with an appropriatealcohol, thiol, or amine of formula R³ XH to obtain the carbamoylcompound (V). Preferably the reaction is carried out in a solvent; thesolvent should be an aprotic solvent to avoid reaction of the solventwith the bromo-compound (IV). Preferably an acid acceptor is present inat least a stoichiometric proportion. Examples of acid acceptors includetertiary amines, for example triethylamine and pyridine. The reactiontakes place readily even at ambient temperatures but may be acceleratedif desired by heating for example to 100° C. or above.

The intermediate compounds of formula IV and V are novel and constitutea further aspect of the present invention.

The final step (d) of Scheme A is the treatment of the carbamoylcompound (V) with a dehydrating agent to convert it to the correspondingcyano compound. The dehydrating agent may be, for example, a bi-molaramount of p-toluene sulphonyl chloride in pyridine as solvent and acidacceptor, or another dehydrating agent, for example phosphorusoxychloride-dimethylformamide. The reaction with p-toluenesulphonylchloride proceeds readily at ambient temperature. Scheme A has beendescribed in terms of brominated compounds; however, the scheme couldequally be carried out using a chlorinating agent (e.g. gaseouschlorine) in place of a brominating agent, to produce the chlorinatedcompound corresponding to compound (IV); this could then be used in step(c) in place of compound (IV). This route cannot be used where R¹ isreadily attacked by elemental bromine or chlorine.

A further process for making compounds of the invention in which R² ishydrogen is outlined in Scheme B: ##STR12##

In step (a) of Scheme B, an amide R¹ CONH₂ is condensed with a glyoxylicester HCO--CO₂ R⁶ to give the hydroxy intermediate (VII). The group R⁶is an ester radical, for example an alkyl group of 1 to 4 carbon atoms(e.g. a methyl group). In step (b), the hydroxy intermediate (VII) istreated with a chlorinating agent (e.g. thionyl chloride) to convert itto the chloroderivative (VIII). This is in turn reacted in step (c) withthe appropriate alcohol, thiol, or amine R³ XH to give the ester (IX).Treatment of this with ammonia in step (c) gives the carbamoylderivative (V) which may then be converted to the cyano compound of theinvention by the method of step (d) of Scheme A.

An alternative process for preparing the amide derivatives of theinvention when X=0 in formula I is a variation of the Scheme B processabove. This Scheme B variation is outlined below: ##STR13##

In this modified Scheme B procedure it can be seen that one can proceeddirectly from the hydroxy intermediate (VII) to the ester (IX) in onestep. The ester (IX) is then treated with ammonia, as in step d, toproduce the carbamoyl derivative (V) which in turn is converted to thecyano compound of the invention (VI) by means of the final step (step d)of the process of Scheme A.

A further process for preparing compounds of the invention in which thegroup XR³ is an --NHCOR³ group is outlined in Scheme C below. ##STR14##

According to Scheme C the bromo-amide (IV) (prepared as in Scheme A) isreacted with the appropriate nitrile R³ CN in acetic acid under theconditions of the Ritter reaction to give the amide (X). This is thentreated with a dehydrating agent (e.g. trifluoroacetic anhydride inpyridine) to give the required nitrile (XI).

A further method of preparing the nitriles (XI) is shown in Scheme Dbelow. ##STR15##

In Scheme D, the hydroxy-ester (VII) prepared as in Scheme B is reactedwith the appropriate nitrile R³ CN in the presence of acetic acid andsulphuric acid (Ritter reaction) to give the amide (XII). This may thenbe reacted with ammonia to give the amide (X) already prepared in SchemeC. As in Scheme C the amide (X) may then be dehydrated to give therequired nitrile (XI). The conversion of (XII) to (X) may be troublesomebecause the esters (XII) tend to be highly insoluble.

A further method of preparing compounds of the invention is outlined inScheme E. ##STR16##

According to Scheme E, an amide R¹ CONHR² is first treated with sodiumhydride and the anion so generated is then reacted with an alpha bromoester R³ X--CH(Br)CO₂ R⁶ to give the ester (XIII). This is then reactedwith ammonia to give the amide (XIV), and finally (XIV) is treated witha dehydrating agent to give the nitrile (XV).

This method may conveniently be used to prepare compounds in which R² isother than hydrogen, particularly when either R¹ or R² is susceptible toreaction with bromine or sulphuryl chloride, which are used as reagentsin certain other routes described herein.

A further method for preparing compounds of the invention is outlined inScheme F. ##STR17##

According to Scheme F, an amine R² NH₂ is condensed with formaldehydecyanhydrin to give the substituted aminoacetonitrile R² NHCH₂ CN. Thisis then acylated by the appropriate acid chloride R¹ COCl to give theamide derivative (XVI).

This in turn is chlorinated (e.g. with SO₂ Cl₂) or brominated (e.g. withBr₂) to give the highly reactive bromo- or chloro-derivative (XVII).This is treated with the appropriate alcohol, thiol or amine R³ XH inthe presence of base to give the required nitrile (XV).

The chloro- or bromo-nitriles (XVII) are too unstable to be isolated andcharacterised, and are used within a short time after they are prepared.The final stage (d) of the scheme may conveniently be carried out byusing an excess of the alcohol, thiol, or amine R³ XH as solvent, andanhydrous potassium carbonate as the base. Triethylamine or othertertiary amines may also be used as the base.

The cyanoamides (XVI) may also be prepared by methods other than thatdescribed above. Thus, the R² substituent may be introduced byalkylation as shown below: ##STR18## Another alternative is shown below:##STR19##

Compounds of the invention in which the group E is a thiocarbamoylradical may be prepared according to Scheme G below: ##STR20##

The reaction is conveniently carried out by passing gaseous H₂ S througha solution of the nitrile in pyridine containing a little triethylamineas catalyst. Usually the solution is externally cooled to 0°-10°. If theproduct does not separate from the solution, it may be isolated byremoval of the solvent.

The amide derivatives of formula I, and compositions containing them,are variously active against a wide range of fungal diseases,particularly, for example, against:

Plasmopara viticola (downy mildew) on vines and

Phytophthora infestans (late blight) on potatoes and tomatoes and otherspecies of Phytophthora

Phytophthora parasitica, Phytophthora cinnamomi,

Phytophthora palmivora and Phytophthora capsici on a range ofcommercially important crops

Peronospora tabacina on tobacco

Peronospora parasitica on cabbage

Peronospora destructor on onions

Bremia lactuca on lettuce

Pythium species on a range of commercially important crops

Other fungal diseases, for example:

Venturia inaequalis (scab) on apples

Cercospora arachidicola on peanuts and other Cercospora species.

A particularly valuable feature of the activity of the amide derivativesis their systemic effect, i.e. their ability to move in a plant tocombat an infection or infestation remote from the site of initialapplication. Thus a derivative, or a composition containing it, may beapplied to the soil surrounding the roots of a plant or to the seed orto other plant areas, e.g. leaves, and be taken up by the plant throughits roots, or other areas, to combat fungi locally or elsewhere on theplants.

In another aspect, therefore, the invention provides a process forcombatting fungi, especially of inhibiting the growth of fungi onplants, which comprises applying to the plants, or the locus thereof, afungicidally effective amount of a compound of the formula (I) ashereinbefore defined. The amount of the compound may vary, dependingupon the identity of the particular compound chosen, the fungal specieswhose growth is to be inhibited, and the plant or locus involved. Theskilled worker in the fungicide art will readily be able to establishappropriate application rates by standard procedures without undueexperimentation.

Preferred compounds for use in the fungicidal compositions of theinvention and the process for combatting fungi are those defined indetail above with reference to formula I wherein R₂ is hydrogen, R¹ isoptionally-substituted phenyl, or heterocyclyl, for example 2-furyl, Xis O or S (X is preferably O) and R³ is alkyl, alkenyl, or haloalkyl,and E is CN or CSNH₂.

Preferred phenyl substitution, when R¹ is phenyl, is at the 3, 4 or 5positions and is alkyl, alkoxy, methylenedioxy or halogen. Preferredalkyl groups for R³ are C₁₋₄ alkyl. Allyl is also a preferred group forR³.

The compounds used in the process and compositions of the invention arepreferably applied in the form of a composition, in which the activeingredient is mixed with a carrier comprising a solid or liquid diluent.In another aspect, therefore, the invention provides a fungicidalcomposition, comprising as an active ingredient a compound of theformula (I) as hereinbefore defined, in admixture with a solid or liquiddiluent. Preferably the composition also comprises a surface-activeagent.

The amide derivatives may be used as such for anti-fungal purposes butare more conveniently formulated into compositions for such usage.

The invention also provides fungicidal compositions comprising as activeingredient an amide derivative as defined in any of the paragraphsabove.

The amide derivatives and compositions containing them can be used tocombat plant fungi and treat plants or seeds in a number of ways, forexample they can be applied, formulated or unformulated, directly to thefoliage of a plant which is infected or likely to become infected, orthey can be applied also to bushes and trees, to soil or to other mediumin which plants, bushes or trees are growing or to be planted, or theycan be sprayed on, dusted on or applied as a cream or paste formulation.Application can be to any part of the plant, bush or tree, for exampleto the foliage, stems, branches, seeds or roots, or to the soilsurrounding the roots.

The terms "combatting" and "treatment" as used herein embrace all theforegoing modes of application and the term "plant" includes seedlings,bushes and trees. Furthermore, the method of the invention includesprotectant, prophylactic and eradicant treatment.

The derivatives are preferably used for agricultural and horticulturalpurposes in the form of compositions. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dusting powders or granules, forexample ordinary grains or "slow release" granules wherein the activeingredient is mixed with a solid diluent or carrier, for example,kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc,powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceousearth and China clay. Compositions for dressing seed may, for example,comprise an agent (for example a mineral oil) for assisting the adhesionof the composition to the seed.

The compositions may also be in the form of dispersible powders orgrains comprising a wetting agent to facilitate the dispersion inliquids of the powder or grains which may contain also fillers andsuspending agents.

The aqueous dispersion of emulsions may be prepared by dissolving theactive ingredient(s) in an organic solvent which may contain wetting,dispersing or emulsifying agent(s) and then adding the mixture soobtained to water which may also contain wetting, dispersing oremulsifying agent(s). Suitable organic solvents are ethylene dichloride,isopropyl alcohol, propylene glycol, diacetone alcohol, toluene,kerosene, methylnaphthalene, xylenes and trichloroethylene.

The compositions for spraying may also be in the form of aerosolswherein the formulation is held in a propellant, e.g.fluorotrichloromethane or dichlorodifluoromethane.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The derivatives can be used in smoke generators and also as mixtureswith fertilisers (e.g. nitrogen- or phosphorus- containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the derivative, are preferred.

The invention therefore also provides a fertiliser compositioncomprising the derivative and a fertiliser.

The compositions may also be in the form of liquid preparations for useas dips or sprays which are generally aqueous dispersions or emulsionscontaining the active ingredient in the presence of one or more surfaceactive agent(s), dispersing agent(s), emulsifying agent(s) or anionic ornon-ionic agents. Suitable cationic agents are quaternary ammoniumcompounds for example, cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters ofsulphuric acid (for example sodium lauryl sulphate), and salts ofsulphonated aromatic compounds (for example sodiumdodecylbenzene-sulphonate, sodium, calcium or ammonium lignosulphonate,butylnaphthalene sulphonate, and a mixture of sodium di-isopropyl- andtriisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, orwith alkyl phenols such as octylphenol, nonylphenol and octylcresol.Other non-ionic agents are the partial esters derived from long chainfatty acids and hexitol anhydrides, the condensation products of thesaid partial esters with ethylene ocide, and the lecithins. Suitablesuspending agents are hydrophilic colloids (for examplepolyvinylpyrrolidone and sodium carboxymethylcellulose), and thevegetable gums (for example gum acacia and gum tragacanth).

The compositions for use as aqueous dispersions or emulsions aregenerally supplied in the form of a concentrate containing a highproportion of the active ingredient(s), the concentrate to be dilutedwith water before use. These concentrates often should be able towithstand storage for prolonged periods and after such form aqueouspreparations which remain homogenous for a sufficient time to enablethem to be applied by conventional spray equipment. The concentrates mayconveniently contain 10-85%, generally 25-60%, by weight of the activeingredient(s).

When diluted to form aqueous preparations, such preparations may containvarying amounts of the active ingredient(s) depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient(s) may be used.

The compositions of this invention can comprise also other compound(s)having biological activity, e.g. compounds having similar orcomplementary fungicidal or plant growth regulating activity orcompounds having herbicidal or insecticidal activity.

The other fungicidal compound can be for example one which is capable ofcombating ear diseases of cereals (e.g. wheat) such as Septoria,Gibberella and Helminthosporium spp., seed and soil borne diseases anddowny and powdery mildews on grapes and powdery mildew and scab on appleetc. These mixtures of fungicides can have a broader spectrum ofactivity than the compound of general formula (I) alone; further theother fungicide can have a synergistic effect of the fungicidal activityof the compound of general formula (I). Examples of the other fungicidalcompound are imazalil, benomyl, carbendazim (BCM), thiophanate-methyl,captafol, captan, sulphur, dithiocarbamates, carbathiins, copperoxychloride, triforine, dodemorph, tridemorph, dithianon, pyrazophos,binapacryl, quinomethionate, panoctine, furalaxyl, aluminiumtris(ethylphosphonate), DPX3217, ethirimol, dimethirimol, bupirimate,chlorothalonil and metazanine.

Suitable insecticides are pirimor, croneton, dimethoate, metasystox andformothion.

The other plant growth regulating compound can be one which controlsweeds or seedhead formation, improves the level or longevity of theplant growth regulating activity of the compounds of general formula(I), selectively controls the growth of the less desirable plants (e.g.grasses) or causes the compound of general formula (I) to act faster orslower as a plant growth regulating agent. Some of these other agentswill be herbicides. Examples of suitable agents are the gibberellins(e.g. GA₃, GA₄ or GA₇), the auxins (e.g. indoleacetic acid,indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), thecytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine orBAP), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoicacids (e.g. TIBA), morphactins (e.g. chlorfluorecol), maleic hydrazide,glyphosate, glyphosine, long chain fatty alcohols and acids (e.g. OffShoot O or Off Shoot T), dikegulac, Sustar, Embark, substitutedquaternary ammonium and phosphonium compounds (e.g. CCC or Phosfon-D),Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol,RH531, hydroxybenzonitriles (e.g. bromoxynil), Avenge, Suffix orLontrel.

The invention is illustrated by the following Examples, in which unlessotherwise stated all parts are by weight and temperatures in degreesCentigrade. The Examples that describe chemical syntheses give detailsin some cases of the nuclear magnetic resonance (NMR) spectra of thecompounds. The information given is the chemical shift (δ) for each peakin the spectrum together with a symbol to indicate that nature of thepeak, as follows: s(singlet); d(doublet); m(multiplet); q(quartet);t(triplet). The solvent used was fully deuterated dimethyl sulphoxide ordeuterochloroform (CDCl₃).

EXAMPLE 1

This Example illustrates the preparation of compound no.4 of Table I bythe process of Scheme A.

(a) Preparation of Benzoylamino(bromo)acetamide

To a suspension of benzoylaminoacetonitrile (5 g) in stirred glacialacetic acid (50 ml) was added all at once bromine (5.0 g). After a briefinduction period, the bromine colour was discharged and the product (5.8g) precipitated from the acetic acid. The product was filtered off,washed with glacial acetic acid, and then with anhydrous ether, anddried. A sample crystallised from glacial acetic acid had m.p. 157°(dec.).

Found: C, 42.22; H, 3.7; N, 10.81 C₉ H₉ BrN₂ O₂ requires: C, 42.02; H,3.5; N, 10.89%.

(b) Preparation of Benzoylamino(ethoxy)acetamide

The foregoing bromoamide (13.4 g) was suspended in anhydrous ethanol (50ml) and heated on a steam bath just long enough for it to dissolve (ca.5 min), whereupon the solution was cooled. The ethanol was removed undervacuum and the residual heavy oil was dissolved in water (40 ml) andneutralised by the cautious addition of solid sodium bicarbonate. Thesolution was then extracted with chloroform (200 ml) and the dried(MgSO₄) extract evaporated to yield a white solid. Crystallisation ofthis from dichloromethane-hexane gave the product (7.7 g), m.p.148°-150°.

Found: C, 59.19; H, 6.27; N, 12.5 C₁₁ H₁₄ N₂ O₃ requires: C, 59.45; H,6.34; N, 12.6% δ(DMSO-d₆): 1.15 (t, 3H), 3.55 (q, 2H), 5.55 (d, 1H),7.2-8.0 (m, 7H), 9.0 (d, 1H).

(c) Preparation of Benzoylamino(ethoxy)acetonitrile (Compound No. 4)

A solution of the foregoing ethoxyamide (5.55 g) in anhydrous pyridine(40 ml) containing p-toluenesulphonyl chloride (4.78 g) was kept at roomtemperature for 72 hours. The reaction mixture was diluted with water(200 ml) and the precipitated solid filtered off, washed with water anddried. Crystallisation of the solid from carbon tetrachloride gave theproduct (2.5 g), m.p. 107°-110°.

Found: C, 64.31; H, 6.3; N, 13.54 C₁₁ H₁₂ N₂ O₂ requires: C, 64.69; H,5.92; N, 13.71% δ(CDCL₃): 1.25 (t, 3H), 3.8 (q, 2H), 6.3 (d, 1H),7.4-8.0 (m, 6H).

EXAMPLE 2

This Example illustrates the preparation of compound no.38 of Table I bythe process of Scheme B.

(a) Preparation of Methyl-[3-Methoxybenzoylamino (hydroxy)] acetate

3-Methoxybenzamide (13.25 g) and methyl glyoxylate (7.72 g) in toluene(150 ml) were heated under reflux in a DeanStark apparatus for 6 hours.On cooling the mixture the product separated and was crystallised fromtoluene. Yield, 12.0 g, m.p. 93°-94°.

Found: C, 55.45; H, 5.37; N, 6.3 C₁₁ H₁₃ NO₅ requires: C, 55.23; H,5.43; N, 5.85%.

(b) Preparation of 3-Methoxybenzoylamino(ethoxy)acetamide

The foregoing ester (5.0 g) and thionyl chloride (40 ml) were stirredtogether for 2 hours., after which the excess of thionyl chloride wasremoved under vacuum. The residue was dissolved in ethanol (100 ml) andthe solution then evaporated under vacuum. The residual oil was treatedwith aqueous ammonia (d 0.88) and the mixture allowed to stand. Thesolid so formed was filtered off, dried, and crystallised fromchloroform-light petroleum to give the product (1.8 g), m.p. 143°-144°.

Found: C, 56.17; H, 6.49; N, 10.73 C₁₂ H₁₆ N₂ O₄ requires: C, 57.14; H,6.35; N, 11.11% δ(DMSO-d₆): 1.3 (t, 3H), 3.7 (q, 2H), 4.0 (s, 3H),5.7(d,1H), 7.2-7.8 (m, 6H), 9.15 (d, 1H).

(c) Preparation of 3-Methoxybenzoylamino(ethoxy)acetonitrile

The foregoing ethoxyamide (1.0 g), p-toluenesulphonyl chloride (1.28 g)and pyridine (20 ml) were allowed to stand at room temperature for 72hrs. The reaction was then worked up as described in paragraph (c) ofExample 1. The product (0.7 g) was crystallised from chloroform-lightpetroleum and had m.p. 72°.

δ(CDCl₃): 1.2 (t, 3H), 3.7 (q, 2H), 3.8 (s, 3H), 6.2 (d, 1H), 7-7.6 (m,5H).

EXAMPLE 3

This Example illustrates the preparation of compound no. 53 of Table 1,using the process of Scheme F.

Preparation of N-Methylbenzoylamino(methoxy)acetonitrile

To a cooled (5°-10°) and stirred solution ofN-methylbenzoylaminoacetonitrile (5.0 g) in anhydrous carbontetrachloride (75 ml) was added dropwise bromine (4.6 g). Following theaddition the mixture was stirred for a further 5 min. at roomtemperature, when methanol (25 ml) was added all at once. After stirringthe mixture for a further 5 min., triethylamine (5.81 g) was added tothe mixture. The solution was then washed with water and the organicphase dried (MgSO₄) and evaporated. The residual oil was chromatographedon a dry silica column using ether-hexane (7:3) as an eluent. Separationof the major band from the column gave the product as a colourless oil(1.0 g) n_(D) ²¹ 1.5233.

δ(CDCl₃): 3.1 (s, 3H), 3.4 (s, 3H), 6.0 (very broad, 1H), 7.4 (s, 5H).

EXAMPLE 4

This Example illustrates the preparation of compound no.40 of Table I,using the process of Scheme A.

(a) Preparation of 3-Chlorobenzoylamino(methylthio)acetamide

To a solution of 3-chlorobenzoylamino(bromo)acetamide (5.5 g) inanhydrous tetrahydrofuran (100 ml) containing methyl mercaptan (slightexcess) was added 1 equivalent of triethylamine and the mixture kept for72 hrs. The solution was filtered and the filtrate evaporated to give anoil which solidified on treatment with ether. Crystallisation of thesolid from ethyl acetate gave the product (0.67 g).

δ(DMSO-d₆): 2.06 (s, 3H), 5.6 (d, 1H), 7.4-7.8 (m, 6H), 8.9 and 9.2 (twodoublets, 1H).

(b) Preparation of 3-chlorobenzoylamino(methylthio)acetonitrile(Compound No.40)

The foregoing amide (0.67 g) and 2 equivalents of p-toluenesulphonylchloride in pyridine (10 ml) were kept at room temperature for 48 hrs.The mixture was then poured into water (100 ml). The solid whichseparated was dried, and crystallised from chloroform-light petroleum togive the product (0.1 g), m.p. 115°-117°.

Found: C, 48.99; H, 3.71; N, 11.01 C₁₀ H₉ ClN₂ OS requires: C, 49.9; H,3.77; N, 11.64% δ(CDCl₃): 2.35 (s, 3H), 6.05 (d, 1H), 7.8-7.2 (m, 5H).

EXAMPLE 5

This Example illustrates the preparation of compound no 158 of Table 1by the process of Scheme C.

(a) Preparation of Acetylamino(3,5-dimethylbenzoylamino)acetamide

To a suspension of 3,5-dimethylbenzoylaminoacetonitrile (1 g) in glacialacetic acid (20 ml) was added all at once bromine (0.85 g). Afterstirring the mixture at room temperature for 15 min. the white solid wasseparated, washed with anhydrous ether and then re-suspended in glacialacetic acid (10 ml). To this was added concentrated sulphuric acid (1.5ml) and acetonitrile (8 ml). After 1 hour the mixture was poured intowater (30 ml) and extracted with chloroform (2×30 ml). The dried (MgSO₄)extract was evaporated and the residue crystallised from aqueous ethanolto give the product (0.38 g) as a white solid (Compound No 154 of TableI), m.p. 244°-5°.

Found: C, 58.49; H, 6.42; N, 15.46 C₁₃ H₁₇ N₃ O₃ requires: C, 59.13; H,6.46; N, 15.97% δ(DMSO-d₆): 1.9 (3H,s), 2.3 (6H,s), 5.8 (1H,dd), ca.7.1-7.5 (5H,m), 8.3 (1H,d), 8.7 (1H,d).

(b) Preparation of Acetylamino (3,5-dimethylbenzoylamino)acetonitrile

The foregoing acetamide (1.0 g) was dissolved in anhydrous pyridine (25ml) which was then cooled to -25°. Trifluoroacetic anhydride (1.5 g) wasadded dropwise to the cooled and stirred solution, and following theaddition the solution was allowed to come to 0° whereupon it was pouredinto water (70 ml) and extracted with ether (2×50 ml). Evaporation ofthe ethereal extracts and crystallisation of the residue from ethylacetate-hexane gave the product (0.6 g) as a pale cream solid, m.p.195°-7°.

Found: C, 62.51; H, 5.98; N, 17.16 C₁₃ H₁₅ N₃ O₂ requires: C, 63.67; H,6.12; N, 17.14% δ(DMSO-d₆): 1.8 (3H,s), 2.2 (6H,s), 6.2 (1H,dd), 7.1(1H,s), 7.4 (2H,s), 9.1 (1H,s), 9.5 (1H,s).

EXAMPLE 6

This Example illustrates the preparation of compound No. 153 of Table Iby the process of Scheme D.

(a) Preparation of Methyl Acetylamino(3,5-dichlorobenzoylamino)acetate

A mixture of 3,5-dichlorobenzamide (19.0 g) and methyl glyoxylate (8.8g) in ethyl acetate (300 ml) was heated under reflux for 8 hours. Thesolvent was removed and the residual adduct was crystallised fromchloroform-light petroleum. A portion (4.0 g) of the adduct wasdissolved in a mixture of glacial acetic acid (30 ml) and acetonitrile(10 ml) with stirring, and then concentrated sulphuric acid (4 ml) wasadded. The mixture was kept at room temperature overnight when water(100 ml) was added. The precipitated solid was washed with water, dried,and crystallised from ethanol to give the product (2.45 g) as acolourless crystalline solid, m.p. 235°-237°.

Found: C, 45.24; H, 3.88; N, 8.84 C₁₂ H₁₂ Cl₂ N₂ O₄ requires: C, 45.14;H, 3.76; N, 8.77% δ(DMSO-d₆): 1.95 (3H,s), 3.7 (3H,s), 5.9 (1H,dd), 7.95(3H,m), 8.9 (1H,d), 9.75 (1H,d).

(b) Preparation of Acetylamino (3,5-dichlorobenzoylamino)acetamide

The foregoing ester (1.46 g) was dissolved in dimethylformamide (70 ml)which was then saturated with ammonia (gas) and the mixture kept for 7days. The solvent was removed under reduced pressure and the residuecrystallised from aqueous dimethylformamide to give the product (0.72g), m.p. 267°-268° (dec).

Found: C, 43.62; H, 3.72; N, 13.82 C₁₁ H₁₁ Cl₂ N₃ O₃ requires: C, 43.42;H, 3.62; N, 13.82% δ(DMSO-d₆): 1.95 (3H,s),5.9 (1H,dd), 7.3 (2H,d,broad)7.6 (1H,m), 7.9 (2H,m), 8.35 (1H,d), 9.2 (1H,d).

(c) Preparation of Acetylamino (3,5-dichlorobenzoylamino)acetonitrile

The foregoing acetamide (0.5 g) in anhydrous pyridine (10 ml) at -25°was treated with trifluoroacetic anhydride as described above. Theproduct (0.18 g), crystallised from aqueous dimethylformamide, had m.p.227°-228°.

Found: C, 45.95; H, 3.12; N, 14.43; C₁₁ H₉ Cl₂ N₃ O₂ requires: C, 46.15;H, 3.15; N, 14.68% δ(DMSO-d₆): 1.95 (3H,s), 6.4 (1H,dd), 7.9 (3H,m),9.35 (1H,d), 10.0 (1H,d).

EXAMPLE 7

This Example illustrates the preparation of compound no.159 of Table Iby the process of Scheme E.

(a) N-Furfuryl-3,5-dichlorobenzamide

To a vigorously stirred solution of furfurylamine (2.78 g) in ethylacetate (40 ml) was added sodium hydroxide (1.15 g) in water (45 ml),followed immediately by the addition of a solution of3,5-dichlorobenzoyl chloride (6.0 g) in ethyl acetate (20 ml). Followingthe mild exothermic reaction the ethyl acetate layer was removed, dried(MgSO₄), and evaporated. Crystallisation of the residue from cyclohexanegave the product (6.6 g) as colourless needles.

(b) Preparation ofN-Furfuryl-3,5-dichlorobenzoylamino(methoxy)acetonitrile

To a stirred suspension of sodium hydride (0.58 g) in anhydroustetrahydrofuran (40 ml) was added in portions the foregoing amide (3.0g). Following the addition and cessation of hydrogen evolution was addedwith stirring methyl 2-bromo-2-methoxy acetate (2.04 g) and the mixturestirred for a further 2 hours at room temperature. Water (100 ml) wasthen added and the solution extracted with methylene chloride (3×50 ml)and the extracts dried and evaporated. The resultant crude oily esterwas dissolved in methanol (20 ml) which was then saturated with ammoniagas and kept overnight. The solvent was removed under reduced pressureand the residual oil triturated with ether to give crude amide (1.91 g).The crude amide (1.75 g) was dissolved in anhydrous pyridine (10 ml),cooled to 0° with stirring and phosphorus oxychloride (0.84 g) addeddropwise so that the temperature of the mixture did not exceed 0°. After25 minutes at 0°, water (100 ml) was added and the mixture was extractedwith ether (40 ml). The dried (MgSO₄) ether extract was chromatographedon silica using diisopropyl ether as the eluent. Following elution fromthe column and evaporation of the solvent the product (1.24 g) wasobtained as a colourless oil which slowly crystallised, m.p. 89°-90°.

δ(CDCl₃): 3.4 (3H,s), 4.65 (2H,s), 6.1 (1H,s,broad) 6.3 (2H,m), 7.3-7.5(4H,m).

EXAMPLE 8

This Example illustrates the preparation of compound no.142 of Table Iby the process of Scheme F.

Preparation of N-Benzyl-3,5-dimethylbenzoylamino(methoxy)acetonitrile

To a stirred solution of glycollonitrile (25 g) in methanol was addeddropwise over 45 minutes benzylamine (46.9 g) keeping the temperature ofthe reaction between 15°-20°. Following the addition the reactionmixture was kept overnight at room temperature, and then distilled togive benzylaminoacetonitrile (42.0 g) as a colourless oil, b.p. 120°/15mm. Reaction of this (3.0 g) with 3,5-dimethylbenzoyl chloride (3.46 g)as described above gave crudeN-benzyl-3,5-dimethylbenzoylaminoacetonitrile (5.81 g) as a colourlessviscous oil which was used in the next stage without furtherpurification. To this crude amide (2.0 g) in anhydrous methylenechloride (8 ml) was added sulphuryl chloride (0.97 g). Following thecessation of gas evolution (ca. 15 min.), anhydrous methanol (20 ml) andfinely powdered anhydrous potassium carbonate (1.95 g) was added to themixture which was then stirred for 30 minutes. Solids were removed fromthe solution which was then evaporated and the residual oilchromatographed on a column of silica using methylene chloride as aneluent. Following elution from the column and evaporation of thesolvent, the product (1.2 g) was obtained as a very pale-yellow viscousoil.

Found: C, 73.87; H, 6.67; N, 9.22 C₁₉ H₂₀ N₂ O₂ requires: C, 74.02; H,6.49; N, 9.09%

(CDCl₃): 2.28 (6H,s), 3.25 (3H,s), 4.75 (2H,s), 5.85 (1H,s,broad), ca.7.0-7.4 (8H,m).

EXAMPLE 9

This Example illustrates the preparation of compound No. 84 of Table Iby the process of Scheme G.

Preparation of 3-chlorobenzoylamino(ethoxy)thioacetamide

Into a solution of 3-chlorobenzoylamino(ethoxy) acetonitrile (1 g) intoluene (50 ml) containing triethylamine (1 g) was passed hydrogensulphide gas. The precipitated product (0.72 g) was collected andcrystallised from chloroform-light petroleum. m.p. 136°-137°.

Found: C, 48.53; H, 4.84; N, 10.19 C₁₁ H₁₈ ClN₂ O₂ S requires: C, 48.44;H, 4.80; N, 10.27%.

EXAMPLE 10

This Example illustrates the herbicidal properties of compounds of TableI. The compounds were submitted to herbicide tests as described below.

Each compound was formulated for test by mixing an appropriate amount ofit with 5 ml of an emulsion prepared by diluting 160 ml of a solutioncontaining 21.8 grams per litre of Span 80 and 78.2 grams per litre ofTween 20 in methylcyclohexanone to 500 ml with water. Span 80 is a TradeMark for a surface-active agent comprising sorbitan monolaurate. Tween20 is a Trade Mark for a surface-active agent comprising a condensate of20 molar proportions of ethylene oxide with sorbitan monolaurate. Themixture of the compound and the emulsion was then shaken with glassbeads and diluted to 44 ml with water. The spray composition so preparedwas sprayed on to young pot plants (post-emergence test) of the speciesnamed in Tables 2 and 3 below, at a rate equivalent to 1000 liters perhectare. Damage to plants was assessed 13 days after spraying bycomparison with untreated plants, on a scale of 0 to 5 where 0 is 0 to20% damage and 5 is complete kill. In the table of results, a dash (-)means no test was made.

A test was also carried out to detect pre-emergence herbicidal activity.Seeds of the test species were placed on the surface of fibre trays ofsoil and were sprayed with the compositions at the rate of 1000 litresper hectare. The seeds were then covered with further soil. 20 daysafter spraying, the seedlings in the sprayed fibre trays were comparedwith the seedlings in unsprayed control trays, the damage being assessedon the same scale of 0 to 5.

The results of the tests are given in Tables 2 and 3 below.

                                      TABLE 2                                     __________________________________________________________________________            RATE OF  PRE-OR                                                       COMPOUND                                                                              APPLICATION                                                                            POST-EMERGENCE                                                                            TEST PLANTS                                      NO      kg/ha    APPLICATION Sb                                                                              Rp                                                                              Ct                                                                              Sy                                                                              Mz Ww Rc                                                                              Sn                                                                              Ip                                                                              Am Pi                                                                              Ca                      __________________________________________________________________________    2       5.0      Pre         2 3 1 4 2  5  2 2 --                                                                              0  4 --                                       Post        2 2 0 2 4  4  2 0 1 4  4 --                      4       1.0      Pre         2 4 3 4 5  5  4 1 4 4  4 --                                       Post        0 0 0 2 3  4  1 --                                                                              3 2  3 2                       8       5.0      Pre         1 1 3 3 3  5  0 0 5 2  1 --                                       Post        0 0 0 1 3  4  1 --                                                                              0 1  3 3                       15      1.0      Pre         0 0 0 0 0  4  0 0 0 1  0 0                                        Post        0 0 0 0 0  2  0 0 0 0  0 0                       17      1.0      Pre         0 0 0 0 0  0  0 0 0 0  0 --                                       Post        0 0 0 0 0  0  0 1 1 3  --                                                                              2                       18      0.2      Pre         4 4 1 4 3  5  4 4 0 4  --                                                                              2                                        Post        1 2 0 1 4  3  0 2 3 3  --                                                                              --                      20      1.0      Pre         4 4 4 4 5  5  5 4 3 5  --                                                                              --                                       Post        1 2 0 2 4  4  2 2 3 3  --                                                                              3                       21      1.0      Pre         0 0 0 0 0  5  0 4 0 0  --                                                                              0                       22      0.2      Pre         1 1 0 4 5  5  4 5 0 5  --                                                                              --                                       Post        0 0 0 1 4  4  1 1 --                                                                              3  --                                                                              3                       23      1.0      Pre         0 0 0 1 0  5  0 1 0 0  0 0                                        Post        0 1 0 0 0  0  0 0 3 -- 0 1                       24      5.0      Pre         0 1 2 0 0  4  0 0 0 -- --                                                                              0                                        Post        1 0 0 0 1  2  0 0 3 3  0 3                       26      1.0      Pre         4 4 1 4 2  5  4 4 3 4  --                                                                              3                                        Post        2 2 0 2 4  4  2 2 3 3  --                                                                              3                       28      1.0      Pre         3 1 1 0 0  4  0 0 0 4  --                                                                              0                                        Post        0 0 1 0 1  1  0 0 3 1  --                                                                              --                      30      0.2      Pre         3 2 1 2 2  5  2 0 0 4  --                                                                              4                                        Post        0 0 0 0 3  3  0 2 1 -- --                                                                              2                       31      5.0      Pre         1 0 0 0 0  4  3 0 0 5  5 --                                       Post        0 0 0 1 0  2  1 0 4 0  0 2                       32      3.0      Pre         0 0 1 0 0  4  0 0 0 1  1 --                                       Post        0 0 0 1 0  1  1 0 0 1  0 1                       33      5.0      Pre         3 4 2 4 4  4  4 4 0 5  5 --                                       Post        0 1 1 4 2  3  0 0 3 4  3 4                       34      0.2      Pre         4 4 0 4 3  4  4 4 1 5  --                                                                              3                                        Post        1 1 1 0 3  3  0 2 3 3  --                                                                              --                      36      1.0      Pre         4 4 3 5 4  5  5 4 4 5  5 5                                        Post        3 1 0 2 4  4  2 0 3 3  3 3                       38      1.0      Pre         4 4 3 3 3  5  4 4 3 5  4 5                                        Post        0 0 0 2 4  4  2 0 3 2  2 0                       39      1.0      Pre         5 2 0 3 1  4  3 3 1 5  5 4                                        Post        3 0 1 3 3  3  0 1 4 2  2 2                       40      1.0      Pre         4 4 1 4 5  5  4 5 2 5  5 --                                       Post        0 1 1 3 3  3  2 1 3 1  3 1                       41      0.2      Pre         4 4 0 2 3  5  4 4 1 5  5 --                                       Post        0 0 0 2 2  3  0 0 2 0  2 0                       42      1.0      Pre         4 4 1 4 3  5  5 4 0 5  5 --                                       Post        0 2 0 3 3  4  1 2 3 2  2 1                       43      1.0      Pre         4 2 1 2 3  4  4 4 4 -- 5 5                                        Post        1 0 1 2 2  3  0 0 3 1  2 2                       44      0.2      Pre         4 3 1 3 2  4  3 4 2 -- 5 4                                        Post        0 0 0 3 1  2  1 1 3 1  1 2                       45      1.0      Pre         3 0 0 0 0  2  0 0 0 -- 0 0                                        Post        1 1 0 1 1  0  0 0 0 1  0 1                       46      5.0      Pre         0 0 0 0 0  4  0 3 1 4  0 2                       47      1.0      Pre         0 0 0 0 1  4  1 1 0 -- 5 --                                       Post        0 0 0 0 0  0  0 0 1 3  0 2                       48      5.0      Pre         4 0 1 2 1  5  1 0 0 5  1 4                                        Post        0 0 0 2 0  2  0 0 0 1  1 1                       51      0.05     Pre         0 0 0 1 1  3  0 0 0 -- 1 0                       51      0.2      Pre         3 3 1 3 5  5  3 3 5 -- 5 4                                        Post        1 0 0 3 2  3  0 2 3 4  2 1                       52      0.2      Pre         2 1 0 0 1  5  2 0 5 -- 5 3                                        Post        1 0 1 1 3  3  1 0 3 4  2 2                       53      5.0      Pre         0 0 0 0 0  4  0 2 0 -- 0 0                                        Post        1 0 0 2 0  0  0 1 2 -- 0 4                       54      5.0      Pre         0 0 --                                                                              1 2  5  3 5 4 5  0 1                                        Post        0 0 0 0 2  0  0 1 3 -- 1 1                       55      5.0      Pre         0 0 0 4 4  5  0 1 4 5  5 4                                        Post        0 1 3 1 1  1  0 0 3 -- 2 2                       56      5.0      Pre         0 0 0 0 1  0  0 3 1 0  --                                                                              2                                        Post        0 0 0 0 0  0  0 0 0 -- 0 0                       59      4.0      Pre         2 3 0 2 0  0  0 3 1 -- --                                                                              3                                        Post        0 1 0 0 0  0  0 0 0 -- 0 0                       61      1.0      Pre         5 3 3 4 3  4  4 2 3 5  5 2                                        Post        0 0 0 2 2  3  0 1 3 3  0 3                       62      0.05     Pre         0 0 0 0 0  5  0 1 0 -- 0 0                       62      0.2      Pre         4 2 1 1 3  5  3 1 3 -- 5 5                                        Post        2 0 0 0 3  4  0 0 2 2  2 1                       63      1.0      Pre         3 0 2 1 2  4  2 0 1 -- 2 4                                        Post        1 0 0 0 2  2  1 1 1 0  0 1                       64      1.0      Pre         0 0 0 1 2  2  0 0 0 -- 0 0                       65      1.0      Pre         1 0 0 0 0  0  0 0 0 -- 0 0                       66      0.05     Pre         2 0 0 1 2  3  2 4 0 3  2 2                       66      0.2      Pre         4 2 2 3 5  5  4 4 2 5  5 5                                        Post        2 1 1 3 3  3  0 2 3 1  1 --                      69      1.0      Pre         0 0 0 0 1  2  0 0 0 -- 0 4                                        Post        1 0 0 2 0  1  0 0 0 1  0 1                       70      1.0      Pre         3 2 2 2 2  5  3 4 3 5  5 5                                        Post        0 0 0 1 3  4  1 1 2 2  1 2                       71      1.0      Pre         5 4 1 4 4  5  5 4 3 5  5 5                                        Post        2 2 0 3 4  3  0 1 2 2  1 2                       72      5.0      Pre         1 0 0 0 1  4  1 0 0 -- --                                                                              2                                        Post        0 1 2 0 1  0  0 0 0 -- 1 --                      73      5.0      Pre         0 --                                                                              0 0 0  4  2 0 1 5  4 5                                        Post        0 0 0 2 2  1  0 0 3 3  2 1                       74      1.0      Pre         0 0 0 0 3  5  0 0 0 -- --                                                                              0                                        Post        0 0 0 0 3  0  0 0 1 -- 0 0                       75      5.0      Pre         0 --                                                                              0 0 2  5  0 0 0 1  2 0                                        Post        0 0 0 1 1  0  0 0 0 0  0 0                       78      5.0      Pre         0 --                                                                              0 1 0  4  0 2 0 5  --                                                                              4                                        Post        0 0 0 0 0  1  0 0 0 0  0 0                       81      1.0      Pre         4 3 2 4 3  4  3 4 3 -- --                                                                              4                                        Post        2 1 0 2 3  4  1 1 3 1  1 2                       82      5.0      Pre         0 --                                                                              0 0 0  5  0 1 0 0  1 0                                        Post        0 0 0 0 2  3  0 0 0 0  0 0                       83      1.0      Pre         3 0 1 2 2  3  3 1 0 -- --                                                                              4                                        Post        0 0 0 2 2  0  0 0 3 1  0 2                       84      1.0      Pre         0 0 0 2 1  2  2 0 0 -- --                                                                              0                                        Post        0 0 0 1 2  1  0 0 2 0  1 2                       85      4.0      Pre         2 --                                                                              2 1 2  4  3 1 --                                                                              2  4 0                                        Post        0 1 1 2 1  2  0 1 0 1  0 1                       91      1.0      Pre         5 4 1 3 1  4  2 3 0 5  --                                                                              5                                        Post        --                                                                              2 1 1 3  2  0 2 3 2  1 0                       92      1.0      Pre         3 3 1 3 5  4  4 5 0 5  --                                                                              5                                        Post        --                                                                              1 1 1 3  1  0 0 1 3  0 0                       95      0.2      Pre         5 2 0 2 1  5  3 3 0 5  --                                                                              5                                        Post        --                                                                              0 0 1 2  3  0 1 1 3  0 0                       96      1.0      Pre         4 4 1 3 4  5  3 3 0 5  1 5                                        Post        --                                                                              1 1 2 3  4  1 0 1 3  0 1                       97      1.0      Pre         4 4 4 4 5  5  5 5 4 5  5 5                                        Post        2 3 0 3 4  4  3 4 3 -- 3 2                       98      1.0      Pre         4 4 3 4 5  5  5 4 3 5  5 5                                        Post        2 2 0 2 4  4  2 3 3 -- 2 1                       103     5.0      Pre         4 3 3 3 2  5  2 3 5 -- 1 3                                        Post        1 4 2 3 3  4  1 3 3 -- 3 3                       104     1.0      Pre         0 0 0 0 0  0  0 0 0 0  0 3                                        Post        0 0 0 2 0  0  0 0 0 0  0 0                       106     5.0      Pre         0 0 1 0 0  3  0 0 0 3  0 1                                        Post        0 0 0 0 2  0  0 0 1 0  0 0                       109     1.0      Pre         5 5 2 5 3  5  4 4 5 5  --                                                                              5                                        Post        2 3 1 3 3  3  1 3 3 2  2 3                       __________________________________________________________________________            RATE OF  PRE-OR                                                       COMPOUND                                                                              APPLICATION                                                                            POST-EMERGENCE                                                                            TEST PLANTS                                      NO      kg/ha    APPLICATION Po                                                                              Xs                                                                              Ab                                                                              Cv                                                                              Ot/Av                                                                             Dg Pu                                                                              St                                                                              Ec                                                                              Sh                                                                              Ag                                                                              Cn                      __________________________________________________________________________    2       5.0      Pre         5 1 4 --                                                                              5   5  5 5 5 1 5 3                                        Post        4 2 2 1 4   2  4 4 4 0 3 0                       4       1.0      Pre         4 0 5 --                                                                              5   5  5 4 5 2 5 2                                        Post        2 0 1 3 4   2  4 3 3 3 3 0                       8       5.0      Pre         4 0 4 --                                                                              5   4  4 4 5 1 5 1                                        Post        2 0 1 2 4   3  4 3 3 3 3 2                       15      1.0      Pre         4 0 0 --                                                                              4   0  5 1 0 3 5 1                                        Post        3 0 0 1 2   0  4 2 0 0 3 0                       17      1.0      Pre         0 0 0 --                                                                              0   1  3 0 0 0 0 0                                        Post        0 0 1 2 0   0  0 1 0 1 0 0                       18      0.2      Pre         5 0 5 --                                                                              4   5  5 5 4 4 1 0                                        Post        3 2 2 3 3   4  4 3 1 0 1 0                       20      1.0      Pre         5 0 5 --                                                                              5   5  5 5 5 5 5 3                                        Post        3 2 3 3 4   4  4 4 4 4 3 3                       21      1.0      Pre         --                                                                              0 4 --                                                                              3   1  --                                                                              0 0 0 3 2                       22      0.2      Pre         5 0 4 --                                                                              5   5  5 5 4 3 4 1                                        Post        3 1 1 3 4   4  4 5 2 1 2 0                       23      1.0      Pre         0 0 1 --                                                                              2   0  3 0 0 0 0 0                                        Post        1 0 0 0 0   0  0 0 0 0 1 0                       24      5.0      Pre         3 0 3 --                                                                              4   4  5 4 3 --                                                                              4 --                                       Post        3 0 2 3 3   4  0 1 4 2 0 0                       26      1.0      Pre         5 0 5 --                                                                              5   5  5 5 5 4 4 6                                        Post        1 2 4 --                                                                              4   4  4 4 3 3 2 1                       28      1.0      Pre         4 1 2 --                                                                              2   5  5 4 2 0 0 0                                        Post        1 0 2 3 2   4  2 3 0 1 0 0                       30      0.2      Pre         5 0 4 --                                                                              4   5  5 5 5 2 1 1                                        Post        1 2 3 4 4   4  3 0 0 0 0 --                      31      5.0      Pre         5 0 3 --                                                                              4   2  5 4 2 3 0 0                                        Post        2 0 0 3 3   2  0 2 0 0 0 0                       32      3.0      Pre         3 2 3 --                                                                              3   0  4 0 0 0 0 0                                        Post        0 0 0 0 3   3  0 1 0 1 0 0                       33      5.0      Pre         5 0 4 --                                                                              4   5  5 5 5 4 1 0                                        Post        2 0 2 2 3   4  1 3 3 2 1 0                       34      0.2      Pre         5 0 4 --                                                                              4   5  5 5 4 4 1 2                                        Post        3 1 2 3 3   4  4 3 0 1 2 0                       36      1.0      Pre         5 0 5 --                                                                              5   5  5 5 5 5 4 --                                       Post        3 1 2 1 4   4  4 4 3 4 2 1                       38      1.0      Pre         5 0 4 --                                                                              5   5  5 5 5 5 5 --                                       Post        2 0 2 2 4   4  4 4 4 3 2 0                       39      1.0      Pre         5 0 4 --                                                                              4   5  5 5 5 5 2 --                                       Post        2 1 2 2 3   4  4 4 1 2 0 0                       40      1.0      Pre         5 0 5 --                                                                              4   5  5 5 5 4 4 0                                        Post        2 1 2 2 3   4  4 3 4 3 3 0                       41      0.2      Pre         5 0 5 --                                                                              4   5  5 5 5 4 4 0                                        Post        1 0 0 1 4   4  2 3 3 2 2 0                       42      1.0      Pre         5 2 5 --                                                                              4   5  5 5 4 4 2 1                                        Post        1 2 2 2 3   4  2 2 4 2 2 0                       43      1.0      Pre         5 0 5 --                                                                              4   5  5 5 5 4 5 2                                        Post        1 1 2 3 4   4  3 2 2 1 0 0                       44      0.2      Pre         5 0 4 --                                                                              4   5  5 5 4 4 4 0                                        Post        1 0 2 2 3   4  3 2 0 0 0 0                       45      1.0      Pre         5 0 0 --                                                                              3   3  5 1 0 0 4 0                                        Post        0 0 1 1 0   2  0 0 0 0 0 0                       46      5.0      Pre         2 0 0 --                                                                              4   1  3 2 0 1 1 --                      47      1.0      Pre         5 1 0 --                                                                              3   4  5 2 2 3 0 0                                        Post        0 1 2 1 0   3  0 2 0 1 0 0                       48      5.0      Pre         5 0 4 --                                                                              3   5  5 3 5 1 0 0                                        Post        2 1 1 --                                                                              3   2  1 5 0 0 0 0                       51      0.05     Pre         5 0 4 --                                                                              2   4  5 1 1 2 5 0                       51      0.2      Pre         5 0 5 --                                                                              5   5  5 5 5 5 5 5                                        Post        2 1 2 2 4   4  4 4 1 1 1 0                       52      0.2      Pre         5 0 4 --                                                                              5   4  5 4 4 4 5 1                                        Post        2 1 1 3 4   4  4 3 1 0 3 1                       53      5.0      Pre         0 1 0 --                                                                              5   0  0 0 0 0 0 0                                        Post        1 0 0 0 0   1  0 1 0 0 0 0                       54      5.0      Pre         5 0 3 --                                                                              4   4  5 4 4 3 0 5                                        Post        2 0 1 2 0   1  0 0 1 0 0 0                       55      5.0      Pre         4 0 3 --                                                                              5   5  5 5 5 2 5 0                                        Post        2 0 1 1 4   2  2 1 0 0 1 0                       56      5.0      Pre         --                                                                              0 0 --                                                                              1   1  --                                                                              0 0 0 2 1                                        Post        --                                                                              0 0 --                                                                              0   0  --                                                                              3 0 0 0 0                       59      4.0      Pre         --                                                                              0 2 --                                                                              0   0  --                                                                              1 2 0 3 0                                        Post        --                                                                              0 0 --                                                                              0   0  --                                                                              0 0 0 0 0                       61      1.0      Pre         5 0 5 --                                                                              4   5  5 5 5 3 4 1                                        Post        3 1 2 3 2   4  2 3 3 3 1 0                       62      0.05     Pre         --                                                                              0 0 --                                                                              3   4  5 4 2 0 3 0                       62      0.2      Pre         5 0 4 --                                                                              5   5  5 5 5 1 5 0                                        Post        3 1 2 2 3   4  4 3 1 0 3 1                       63      1.0      Pre         5 0 5 --                                                                              4   4  5 5 5 3 2 0                                        Post        1 0 2 2 1   4  3 4 0 0 2 0                       64      1.0      Pre         2 0 2 --                                                                              3   4  4 3 0 1 0 0                       65      1.0      Pre         3 0 1 --                                                                              0   0  0 1 0 0 0 0                       66      0.05     Pre         3 0 3 --                                                                              3   5  5 4 3 4 1 --                      66      0.2      Pre         5 0 5 --                                                                              5   5  5 5 4 4 3 1                                        Post        2 1 2 --                                                                              4   4  4 3 3 2 2 0                       69      1.0      Pre         --                                                                              0 0 --                                                                              3   4  --                                                                              2 0 0 0 0                                        Post        --                                                                              0 1 --                                                                              0   2  --                                                                              4 0 0 0 0                       70      1.0      Pre         --                                                                              0 4 --                                                                              5   5  --                                                                              5 5 2 5 2                                        Post        --                                                                              0 2 --                                                                              4   4  --                                                                              3 4 1 3 0                       71      1.0      Pre         --                                                                              0 4 --                                                                              5   5  --                                                                              5 5 4 3 1                                        Post        --                                                                              0 1 --                                                                              4   4  --                                                                              4 4 2 2 1                       72      5.0      Pre         --                                                                              0 0 --                                                                              4   3  --                                                                              2 2 2 1 0                                        Post        --                                                                              0 1 --                                                                              0   0  --                                                                              5 3 3 2 0                       73      5.0      Pre         --                                                                              0 4 --                                                                              4   4  --                                                                              4 0 1 1 --                                       Post        --                                                                              0 2 --                                                                              4   2  --                                                                              1 1 0 0 0                       74      1.0      Pre         --                                                                              0 0 --                                                                              3   3  --                                                                              5 3 0 2 0                                        Post        --                                                                              0 0 --                                                                              0   0  --                                                                              0 0 0 0 0                       75      5.0      Pre         --                                                                              1 1 --                                                                              1   0  --                                                                              0 0 2 4 0                                        Post        --                                                                              0 0 --                                                                              0   0  --                                                                              1 1 0 0 0                       78      5.0      Pre         --                                                                              0 0 --                                                                              4   0  --                                                                              3 0 0 4 --                                       Post        --                                                                              0 0 --                                                                              1   0  --                                                                              0 0 0 0 0                       81      1.0      Pre         --                                                                              0 4 --                                                                              5   4  --                                                                              5 5 3 1 0                                        Post        --                                                                              0 1 --                                                                              3   4  --                                                                              3 3 3 2 0                       82      5.0      Pre         --                                                                              0 0 --                                                                              3   1  --                                                                              0 0 0 0 --                                       Post        --                                                                              0 0 --                                                                              1   0  --                                                                              1 0 0 1 0                       83      1.0      Pre         --                                                                              0 2 --                                                                              4   4  --                                                                              3 2 0 1 0                                        Post        --                                                                              0 1 --                                                                              1   2  --                                                                              1 1 1 0 0                       84      1.0      Pre         --                                                                              0 0 --                                                                              3   4  --                                                                              3 1 0 0 0                                        Post        --                                                                              0 2 --                                                                              1   0  --                                                                              2 0 1 0 0                       85      4.0      Pre         --                                                                              0 --                                                                              --                                                                              3   5  --                                                                              4 3 2 0 --                                       Post        --                                                                              0 1 --                                                                              2   3  --                                                                              2 2 0 0 0                       91      1.0      Pre         --                                                                              0 5 --                                                                              5   5  --                                                                              5 5 4 0 --                                       Post        --                                                                              2 2 --                                                                              2   3  --                                                                              1 1 2 0 --                      92      1.0      Pre         --                                                                              0 5 --                                                                              4   5  --                                                                              5 5 1 5 --                                       Post        --                                                                              0 2 --                                                                              3   4  --                                                                              3 0 3 1 --                      95      0.2      Pre         --                                                                              0 4 --                                                                              4   5  --                                                                              5 4 0 0 --                                       Post        --                                                                              1 1 --                                                                              3   1  --                                                                              1 0 1 2 --                      96      1.0      Pre         --                                                                              0 4 --                                                                              5   5  --                                                                              5 5 4 0 --                                       Post        --                                                                              1 2 --                                                                              4   3  --                                                                              3 3 3 2 --                      97      1.0      Pre         --                                                                              4 5 --                                                                              5   5  --                                                                              5 5 4 4 --                                       Post        --                                                                              3 3 --                                                                              4   4  --                                                                              4 4 4 4 --                      98      1.0      Pre         --                                                                              2 4 --                                                                              5   5  --                                                                              5 5 4 4 --                                       Post        --                                                                              2 3 --                                                                              4   4  --                                                                              3 3 3 2 --                      103     5.0      Pre         --                                                                              2 4 --                                                                              5   5  --                                                                              5 4 3 4 --                                       Post        --                                                                              2 2 --                                                                              4   3  --                                                                              3 2 0 2 --                      104     1.0      Pre         --                                                                              0 0 --                                                                              0   0  --                                                                              0 1 0 3 --                                       Post        --                                                                              0 0 --                                                                              0   0  --                                                                              1 0 0 0 --                      106     5.0      Pre         --                                                                              0 1 --                                                                              2   0  --                                                                              0 0 1 5 --                                       Post        --                                                                              0 1 --                                                                              1   1  --                                                                              1 0 0 0 --                      109     1.0      Pre         --                                                                              4 5 --                                                                              4   5  --                                                                              5 5 4 4 --                                       Post        --                                                                              3 3 --                                                                              4   4  --                                                                              2 2 0 2 --                      __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________            RATE OF  PRE- OR                                                      COMPOUND                                                                              APPLICATION                                                                            POST-EMERGENCE                                                                            TEST PLANTS                                      NO      kg/ha    APPLICATION Sb                                                                              Rp                                                                              Ct                                                                              Sy                                                                              Mz Ww Rc                                                                              Sn                                                                              Ip                                                                              Am Pi                                                                              Ca                      __________________________________________________________________________    110     1.0      Pre         4 4 2 4 3  5  2 --                                                                              1 5  --                                                                              5                                        Post        1 1 1 2 1  4  0 1 3 2  --                                                                              1                       111     1.0      Pre         5 4 2 4 3  4  4 3 2 5  --                                                                              5                                        Post        1 1 1 0 2  4  0 2 3 4  --                                                                              2                       112     5.0      Pre         3 2 0 0 0  3  0 2 0 0  --                                                                              1                                        Post        0 0 0 2 1  0  0 0 0 1  --                                                                              0                       117     1.0      Pre         2 1 0 2 0  2  2 2 0 3  --                                                                              5                                        Post        0 0 0 2 0  1  0 1 2 2  --                                                                              2                       119     1.0      Pre         2 0 0 0 0  4  2 1 3 3  --                                                                              4                                        Post        0 0 0 1 1  3  0 0 2 1  --                                                                              0                       120     1.0      Pre         4 3 3 3 3  4  4 4 3 4  --                                                                              4                                        Post        0 1 0 2 2  3  0 1 3 3  --                                                                              2                       122     5.0      Pre         1 0 1 3 0  4  0 0 3 0  --                                                                              --                                       Post        0 0 0 0 0  0  0 1 3 0  --                                                                              0                       125     0.2      Pre         4 1 0 2 2  3  2 1 --                                                                              3  --                                                                              3                       125     1.0      Pre         5 4 3 3 4  4  5 5 --                                                                              5  --                                                                              5                                        Post        2 2 1 2 4  4  2 2 2 -- --                                                                              3                       126     1.0      Pre         4 4 3 4 3  5  5 5 --                                                                              5  --                                                                              5                                        Post        1 2 0 1 3  4  0 2 2 -- --                                                                              3                       127     5.0      Pre         0 0 0 0 0  0  0 0 0 0  --                                                                              0                                        Post        1 3 0 0 2  0  0 0 2 -- --                                                                              --                      134     .025     Pre         1 0 0 2 0  0  0 0 0 0  0 1                       134     1.0      Pre         5 5 4 5 4  5  4 4 4 -- 4                                          Post        3 3 1 3 3  4  4 2 2 3  --                                                                              3                       136     1.0      Pre         3 3 2 1 2  4  5 4 4 3  3 3                       138     5.0      Pre         --                                                                              --                                                                              --                                                                              --                                                                              -- 4  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                       Post        --                                                                              --                                                                              --                                                                              --                                                                              -- 2  --                                                                              --                                                                              --                                                                              -- --                                                                              --                      141     1.0      Pre         4 4 0 4 2  4  3 3 4 3  3 4                                        Post        2 2 0 2 2  2  0 2 2 3  --                                                                              3                       144     1.0      Pre         1 2 0 0 1  2  2 0 3 1  0 1                                        Post        1 1 1 1 2  3  0 0 2 -- 0 0                       146     1.0      Pre         3 2 0 1 1  2  2 0 3 2  3 3                                        Post        0 0 1 0 0  2  0 0 1 -- 0 0                       148     1.0      Pre         0 0 0 0 0  0  1 --                                                                              0 0  0 0                                        Post        0 0 0 1 1  2  0 0 1 -- 1 --                      153     1.0      Pre         2 0 0 1 1  3  1 0 2 3  2 2                                        Post        0 0 1 0 2  2  0 1 2 -- 0 2                       __________________________________________________________________________            RATE OF  PRE- OR                                                      COMPOUND                                                                              APPLICATION                                                                            POST-EMERGENCE                                                                            TEST PLANTS                                      NO      kg/ha    APPLICATION Ga                                                                              Xa                                                                              Ab                                                                              Co                                                                              Av Dg Al                                                                              St                                                                              Ec                                                                              Sh Ag                                                                              Cn                      __________________________________________________________________________    110     1.0      Pre         --                                                                              0 4 3 4  5  5 5 5 3  5 --                                       Post        2 1 2 0 4  3  3 1 2 1  3 --                      111     1.0      Pre         --                                                                              0 4 1 3  5  5 5 5 4  5 --                                       Post        3 1 2 0 4  3  4 3 2 1  2 --                      112     5.0      Pre         --                                                                              0 0 0 0  1  3 3 2 0  --                                                                              --                                       Post        1 1 1 0 1  0  0 2 0 0  0 --                      117     1.0      Pre         --                                                                              0 3 0 0  4  1 1 3 3  2 --                                       Post        1 0 1 1 0  0  0 1 0 0  1 --                      119     1.0      pre         --                                                                              0 2 0 3  4  5 3 2 2  5 --                                       Post        1 0 1 0 3  0  0 0 0 2  3 --                      120     1.0      Pre         --                                                                              0 4 2 2  5  5 5 5 4  5 --                                       Post        2 0 2 1 3  2  0 2 0 1  2 --                      122     5.0      Pre         --                                                                              0 2 0 5  0  5 0 1 1  0 2                                        Post        --                                                                              1 0 0 2  0  0 0 0 0  3 0                       125     0.2      Pre         0 5 --                                                                              1 5  4  5 4 4 5  5 1                       125     1.0      Pre         5 4 --                                                                              5 5  5  5 5 5 5  5 4                                        Post        1 2 2 1 3  3  2 2 3 1  3 0                       126     1.0      Pre         5 4 --                                                                              5 5  5  5 5 5 5  5 4                                        Post        2 2 2 0 4  2  2 3 1 0  2 0                       127     5.0      Pre         --                                                                              0 2 0 3  0  1 0 0 0  2 0                                        Post        2 0 3 1 2  0  --                                                                              --                                                                              0 0  0 0                       134     .025     Pre         --                                                                              --                                                                              1 0 1  0  3 0 0 0  2 0                       134     1.0      Pre         --                                                                              3 5 4 5  5  5 5 5 5  5 5                                        Post        3 2 3 2 4  4  4 4 4 3  3 2                       136     1.0      Pre         1 1 4 4 5  4  5 5 5 5  4 4                       138     5.0      Pre         --                                                                              --                                                                              --                                                                              --                                                                              5  -- --                                                                              --                                                                              --                                                                              -- --                                                                              --                                       Post        --                                                                              --                                                                              --                                                                              --                                                                              1  -- --                                                                              --                                                                              --                                                                              -- --                                                                              --                      141     1.0      Pre         --                                                                              0 5 3 5  5  3 5 5 4  5 2                                        Post        3 0 2 2 3  3  1 2 1 0  1 1                       144     1.0      Pre         0 0 3 1 4  5  5 5 5 5  5 3                                        Post        0 0 1 1 2  1  0 1 0 0  2 1                       146     1.0      Pre         0 0 0 2 3  4  5 2 2 3  4 2                                        Post        0 0 0 0 1  0  0 0 0 0  --                                                                              0                       148     1.0      Pre         0 0 --                                                                              0 0  1  0 0 0 0  0 0                                        Post        2 1 2 1 0  5  1 3 1 0  0 0                       153     1.0      Pre         0 0 --                                                                              0 3  3  1 2 0 0  3 0                                        Post        0 0 1 0 2  2  0 3 0 0  2 0                       __________________________________________________________________________    Names of test plants in Tables 2 and 3                                        Sb    Sugar beet                                                              Rp    Rape                                                                    Ct    Cotton                                                                  Sy    Soya Bean                                                               Mz    Maize                                                                   Ww    Winter wheat                                                            Rc    Rice                                                                    Sn    Senecio vulgaris                                                        Ip    Ipomoea purpurea                                                        Am    Amaranthus retroflexus                                                  Pi    Polygonum aviculare                                                     Ca    Chenopodium album                                                       Po    Portulaca oleracea                                                      Xs and Xa                                                                           Xanthium spinosum                                                       Ab    Abutilon theophrastii                                                   Cv    Convolvulus arvensis                                                    Ot/Av Oats (cultivated in pre-emergence test and                                    Avena fatua (wild oats) in post-emergence                                     test) (Applies to Table 2; in Table 3 only                                    Avena fatua is used)                                                    Dg    Digitaria sanguinalis                                                   Pu    Poa annua                                                               St    Setaria viridis                                                         Ec    Echinochloa crusth-ti galli                                             Sh    Sorghum halepense                                                       Ag    Agropyron repens                                                        Cn    Cyperus rotundus                                                        Ga    Galium aparine                                                          Co    Cassia obtusifolia                                                      Al    Alopecurus myosuroides                                              

EXAMPLE 11

This Example further illustrates the herbicidal properties of compoundsaccording to the invention. Tests were carried out as described inExample 10, but using different ranges of test plants. Thepost-emergence test was slightly different from the one described inExample 10 in that the seeds were sown in trays of soil and covered witha few millimeters of soil before spraying the test compound, whereas inthe previous test the seeds were sprayed directly.

The compounds were formulated in a similar way to that described inExample 10, but using cyclohexanone solution containing Synperonic NPE1800 (a nonyl-phenolpropylene oxide--ethylene oxide condensate) andTween 85 (a condensate of sorbitan tri-oleate with 20 molar proportionsof ethylene oxide) instead of the methylcyclohexanone solution ofsurfactants described in that Example. The damage to the test plants wasassessed on a scale of 0 to 9 where 0 represents 0 to 10% damage to theplant and 9 is 90 to 100% damage. Assessments were made 26 days afterspraying the compounds. The results are given in Tables 4 and 5 below.

                                      TABLE 4                                     __________________________________________________________________________    COM- RATE OF  PRE- OR                                                         POUND                                                                              APPLICATION                                                                            POST-EMERGENCE                                                                             TEST PLANTS                                        NO   kg/ha    APPLICATION  Ww Br                                                                              Pe                                                                              Rp                                                                              Sb                                                                              Lt                                                                              Av Al                                                                              Bt                                                                              Ag                                                                              Ga                                                                              Sm Ca                                                                              Pi                                                                              Ma Sp               __________________________________________________________________________    18   0.2      Pre          6  7 2 8 9 7 9  9 9 6 7 9  9 9 9  6                              Post         8  7 1 0 1 0 8  3 0 5 7 7  4 7 0  --               20   0.1      Pre          8  9 0 0 9 0 9  9 9 9 5 9  9 9 8  3                     0.2      Pre          9  9 2 7 6 5 9  9 9 9 9 9  9 9 8  4                     0.1      Post         8  6 0 0 1 0 3  1 0 1 5 3  3 4 1  4                     0.2      Post         9  8 0 0 1 0 5  5 2 5 7 5  2 9 2  6                     0.4      Post         9  9 3 0 3 0 9  6 7 9 7 7  6 9 3  6                22   0.1      Pre          7  8 0 0 5 1 9  9 9 8 8 8  9 9 7  1                     0.2      Pre          9  9 0 3 8 2 9  9 9 9 9 9  9 9 6  3                     0.1      Post         7  7 0 0 0 0 4  2 2 3 3 1  2 6 0  3                     0.2      Post         9  6 1 0 1 0 5  4 2 5 6 5  4 7 1  3                     0.4      Post         9  7 1 1 1 0 8  8 6 8 7 6  6 7 1  3                __________________________________________________________________________    The names of the test plants in Table 4                                       Ww Winter wheat                                                               Br Barley                                                                     Pe Peas                                                                       Rp Rape                                                                       Sb Sugar beet                                                                 Lt Lettuce                                                                    Av Avena fatua                                                                Al Alopecurus myosuroides                                                     Bt Bromus tectorum                                                            Ag Agropyron repens                                                           Ga Galium aparine                                                             Sm Stellaria media                                                            Ca Chenopodium album                                                          Pi Polygonum aviculare                                                        Ma Matricaria inodora                                                         Sp Sinapis alba                                                           

                                      TABLE 5                                     __________________________________________________________________________             RATE OF                                                              COMPOUND APPLICATION                                                                            TEST PLANTS                                                 NO       kg/ha    Mz                                                                              Rc                                                                              Sy                                                                              Ct                                                                              To                                                                              Sg Eh                                                                              Ip                                                                              Ab                                                                              Se Si                                                                              Ds                                                                              Xa                                                                              Ec Dg                                                                              St                                                                              Sh  Pm                                                                              Cd                                                                              Cn               __________________________________________________________________________     2       1.1      9 7 2 2 5 5  4 1 2 1  2 4 0 1  8 6 2   --                                                                              0 0                 4       1.1      7 8 3 2 5 8  4 6 6 7  7 6 2 3  9 9 4        --                                                                   4        0               18       0.4      0 1 2 1 1 3  2 3 1 2  2 3 0 0  1 5 1        7                                                                    1        0               20       0.2      7 4 2 1 1 4  4 5 2 2  1 5 1 0  8 6 0        5                                                                    0        0               22       0.4      7 7 2 2 1 3  5 6 1 4  4 4 0 3  7 7 4        7                                                                    0        0               __________________________________________________________________________    The names of test plants in Table 5                                           Mz Maize                                                                      Rc Rice                                                                       Sy Soya bean                                                                  Ct Cotton                                                                     To Tomato                                                                     Sg Sorghum                                                                    Eh Euphorbia heterophylla                                                     Ip Ipomoea purpurea                                                           Ab Abutilon theophrasti                                                       Se Sesbania exaltata                                                          Si Sida spinosa                                                               Ds Datura stramonium                                                          Xa Xanthium pensylvanicum                                                     Ec Echinochloa crusth-ti galli                                                Dg Digitaria sanguinalis                                                      St Setaria viridis                                                            Sh Sorghum halepense                                                          Pm Panicum maximum                                                            Cd Cyperus difformis                                                          Cn Cyperus rotundus                                                       

EXAMPLE 12

This Example illustrates a composition according to the invention whichcomprises an emulsifiable concentrate. The following ingredients werethoroughly mixed to give a solution.

    ______________________________________                                        Compound No. 2 of Table I                                                                           10%                                                     Ethylene dichloride   40%                                                     Calcium dodecylbenzenesulphate                                                                       5%                                                     "Lubrol" L            10%                                                     "Aromasol" H          35%                                                     ______________________________________                                    

EXAMPLE 13

A composition in the form of grains readily dispersible in a liquid,e.g. water, was prepared by grinding together the first threeingredients in the presence of added water and then mixing in the sodiumacetate. The resultant mixture was dried and passed through a BritishStandard mesh sieve, size 44-100, to obtain the desired size of grains.

    ______________________________________                                        Compound No. 4 of Table I                                                                              50%                                                  "Dispersol" T            25%                                                  "Lubrol" APN 5           1.5%                                                 Sodium acetate           23.5%                                                ______________________________________                                    

EXAMPLE 14

The following ingredients were ground together to produce a powderformulation readily dispersible in liquids.

    ______________________________________                                        Compound No. 8 of Table I                                                                              45%                                                  "Dispersol" T            5%                                                   "Lissapol" NX            0.5%                                                 "Cellofas" B600          2%                                                   Sodium acetate           47.5%                                                ______________________________________                                    

EXAMPLE 15

The active ingredient was dissolved in acetone and the resultant liquidwas sprayed on to the granules of china clay. The solvent was thenallowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 18 of Table I                                                                          5%                                                      China clay granules  95%                                                      ______________________________________                                    

EXAMPLE 16

A composition suitable for use as a seed dressing was prepared by mixingthe following three ingredients.

    ______________________________________                                        Compound No. 2 of Table I                                                                          50%                                                      Mineral oil           2%                                                      China clay           48%                                                      ______________________________________                                    

EXAMPLE 17

A dusting powder was prepared by mixing the active ingredient with talc.

    ______________________________________                                        Compound No. 4 of Table I                                                                           5%                                                      Talc                 95%                                                      ______________________________________                                    

EXAMPLE 18

A Col formulation was prepared by ball-milling the constituents set outbelow and then forming an aqueous suspension of the ground mixture withwater.

    ______________________________________                                        Compound No. 8 of Table I                                                                          40%                                                      "Dispersol" T        10%                                                      "Lubrol" APN5         1%                                                      Water                49%                                                      ______________________________________                                    

EXAMPLE 19

A dispersible powder formulation was made by mixing together theingredients set out below and then grinding the mixture until all werethoroughly mixed.

    ______________________________________                                        Compound No. 18 of Table I                                                                         25%                                                      "Aerosol" OT/B        2%                                                      "Dispersol" A.C.      5%                                                      China clay           28%                                                      Silica               40%                                                      ______________________________________                                    

EXAMPLE 20

This Example illustrates the preparation of a dispersible powderformulation. The ingredients were mixed and the mixture then ground in acomminution mill.

    ______________________________________                                        Compound No. 20 of Table I                                                                         25%                                                      "PERMINAL" BX         1%                                                      "Dispersol" T         5%                                                      Polyvinylpyrrolidone 10%                                                      Silica               25%                                                      China clay           34%                                                      ______________________________________                                    

EXAMPLE 21

The ingredients set out below were formulated into a dispersible powderby mixing then grinding the ingredients.

    ______________________________________                                        Compound No. 2 of Table I                                                                          25%                                                      "Aerosol" OT/B        2%                                                      "Dispersol" A         5%                                                      China clay           68%                                                      ______________________________________                                    

In Examples 1 to 10 the proportions of the ingredients given are byweight and the Examples were all repeated using, as active ingredient,the other compounds of Table I.

There now follows an explanation of the compositions or substancesrepresented by the various Trade Marks and Trade Names mentioned above.

    ______________________________________                                        LUBROL L        a condensate of nonyl phenol                                                  (1 mole) with ethylene oxide                                                  (13 moles).                                                   AROMASOL H      a solvent mixture of alkyl-                                                   benzenes                                                      DISPERSOL T AND AC                                                                            a mixture of sodium sulphate                                                  and a condensate of formalde-                                                 hyde with sodium naphthalene                                                  sulphonate                                                    LUBROL APN 5    a condensate of nonyl phenol                                                  (1 mole) with ethylene oxide                                                  (5.5 moles)                                                   CELLOFAS B600   a sodium carboxymethyl                                                        cellulose thickener.                                          ______________________________________                                    

EXAMPLE 22

The compounds were tested against a variety of foliar fungal diseases ofplants. The techniques employed were as follows:

The plants were grown in John Innes Potting Compost (No. 1 or 2) in 4 cmdiameter mini-pots. A layer of fine sand was placed at the bottom tofacilitate uptake of test compound by the roots. The test compounds wereformulated either by bead milling with aqueous Dispersol T or as asolution in acetone or acetone/ethanol which was diluted to the requiredconcentration immediately before use. For the foliage diseasessuspensions (100 ppm active ingredient) were sprayed on to the foliageand applied to the roots of the same plant via the soil. Exceptions werethe tests on Plasmopara viticola and Venturia inaequalis in which thecompound was sprayed on to the foliage only. Sprays were applied tomaximum retention, and root drenches were applied to a finalconcentration equivalent to approximately 40 ppm a.i./dry soil. Tween20, to give a final concentration of 0.05% was added when the sprayswere applied to cereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the diseases. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.After inoculation, the plants were put into an appropriate environmentto allow infection to take place and then incubated until the diseasewas ready for assessment.

The period between inoculation and assessment varied from four tofourteen days according to the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace--5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table 6 below.

In the table below the following compounds have been omitted for thereasons stated.

Compounds Nos. 5, 6, 7, 14, 16, 21, 23, 25, 27, 29, 32, 40, 58, 88, 115,123, 140 were not tested at the standard primary screen rate.

Compounds Nos. 135, 136, 138, 142-145, 147, 148 and 160 were not tested.

A dash, thus "-", in the table in any column indicates that theparticular compound was not tested against that particular disease.

An asterisk, thus "*" against the disease grading in the column headed"BOTRYTIS CINEREA (TOMATO)" signifies that the test plant material usedin this instance were grape berries.

                                      TABLE 6                                     __________________________________________________________________________    COM-  PUCCINIA                                                                              ERYSIPHE                                                                             PLASMOPARA                                                                            PHYTOPHTHORA                                                                            BOTRYTIS                                                                             CERCOSPORA                                                                              VENTURIA              POUND RECONDITA                                                                             GRAMINIS                                                                             VITICOLA                                                                              INFESTANS CINEREA                                                                              ARACHIDICOLA                                                                            INEQUALIS             NUMBER                                                                              (WHEAT) (BARLEY)                                                                             (VINE)  (TOMATO)  (TOMATO)                                                                             (PEANUT)  (APPLE)               __________________________________________________________________________    1     0       0      0       2         0      0         2                     2     0       4      3       3         0      3         3                     3     0       0      0       0         0      0         1                     4     0       0      4       4         0      3         0                     8     0       1      4       4         0      3         --                    9     0       0      0       0         0      1         0                     10    0       0      0       0         0      1         0                     11    0       1      0       0         2      0         1                     12    0       0      0       0         0      0         0                     13    0       0      0       0         0      3         0                     15    0       0      0       1         0      2         0                     17    0       0      0       2         0      2         0                     18    0       0      4       4         0      4         0                     19    0       0      2       1         0      0         0                     20    --      4      4       3         1      3         0                     22    0       4      4       4         0      4         4                     24    0       0      4       3         0      0         --                    26    --      --     --      --        --     --        --                    28    0       0      4       3         0      1         0                     30    0       1      4       3         0      3                               31    0       3      4       3         0      3         0                     33    0       3      4       4         0      3         0                     34    0       2      4       4         0      2         2                     35    0       4      4       0         1      --        --                    36    0       4      4       4         1      --        --                    37    0       1      2       0         0      0         0                     38    0       3      4       4         1      --        --                    39    0       0      4       3         --     1         0                     41    0       3      2       4         0      --        --                    42    0       2      4       4         0      --        --                    43    0       3      4       1         1      --        --                    44    0       3      4       4         0      --        --                    45    0       2      4       2         1      --        --                    46    --      0      0       2         0      0         0                     47    --      0      2       3         0      0         1                     48    --      0      0       0         1      2         0                     49    --      0      0       2         0      0         0                     50    0       3      0       0         0      --        --                    51    0       0      4       4         1      --        --                    52    0       0      4       3         1      --        --                    53    --      0      0       0         0      2         0                     54    --      4      0       0         0      0         2                     55    --      4      1       0         0      2         4                     56    0       1      0       0         --     0         0                     57    0       0      0       0         0      0         0                     59    --      --     --      --        --     --        --                    60    0       1      --      2         0      3         0                     61    0       1      --      4         1      4         1                     62    0       1      --      4         2      4         0                     63    0       4      --      4         2      1         0                     64    0       2      --      0         1      1         0                     65    0       2      --      4         1      1         1                     66    0       2      --      4         0      2         1                     67    0       1      0       0         2      0         0                     68    0       --     0       0         0      1         0                     69    0       0      --      3         0      2         0                     70    0       2      0       3         0      4         --                    71    0       3      --      3         0      3         3                     72    0       4      0       0         0      0         1                     73    0       0      0       0         0      1         0                     74    0       1      0       0         0      0         0                     75    0       0      0       0         0      0         0                     76    0       0      0       0         0      0         0                     77    0       0      0       0         0      0         0                     78    0       0      1       0         0      0         0                     79    0       0      0       0         0      0         3                     80    0       0      0       0         0      0         0                     81    0       0      4       3         0      2         0                     82    0       0      1       0         0      0         0                     83    0       0      3       2         0      1         0                     84    0       0      4       1         0      0         0                     85    0       0      4       4         0      0         2                     86    0       0      3       0         0      2         2                     87    --      --     --      --        --     --        --                    89    0       2      0       0         1      0         0                     90    0       0      0       0         0      1         0                     91    0       0      4       4         1      0         0                     92    0       1      4       3         0      0         0                     93    1       3      0       0         3      2         0                     94    --      --     --      --        --     --        13                    95    0       0      4       4         2      0         --                    96    0       0      3       4         0      0         0                     97    0       0      4       4         0      0         0                     98    0       0      4       4         0      0         2                     99    0       0      0       3         0      0         0                     100   0       0      1       0         0      0         0                     101   0       1      0       0         0      0         0                     102   0       0      4       4         0      2         0                     103   0       0      0       0         0      0         2                     104   --      --     --      --        --     --        --                    105   0       0      0       0         0      0         0                     106   0       0      0       0         0      0         0                     107   0       0      0       0         0      0         0                     108   1       0      4       0         0      0         0                     109   0       0      4       4         0      3         0                     110   0       0      4       4         0      0         0                     111   0       0      4       4         0      2         0                     112   0       0      1       0         0      0         0                     113   0       0      0       1         0      0         0                     114   0       0      0       0         --     0         0                     115   0       0      0       1         0      0         0                     117   0       0      4       4         0      2         0                     118   0       0      4       3         0      3         --                    119   0       0      4       3         0      0         0                     120   0       0      4       4         0      2         0                     121   0       0      0       0         0      0         0                     122   0       0      0       0         0      0         0                     124   0       0      2       0         2      0         0                     125   0       0      4       4         0      0         0                     126   0       0      4       3         0      2         0                     127   0       0      0       0         2      0         0                     128   0       0      0       0         1      0         0                     129   1       0      0       0         2      1         0                     130   4       2      3       0         2      2         0                     131   3       0      2       0         1      0         0                     132   --      --     --      --        --     --        --                    133   0       0      0       0         0      2         0                     134   0       1      4       4         0      3         2                     137   0       0      0       --         0*    0         0                     139   0       0      0       --         0*    0         0                     141   0       0      4       --         0*    --        0                     146   0       1      3       2          0*    0         0                     149   0       3      0       0          0*    1         0                     150   0       2      0       0          0*    0         2                     151   0       0      2       1          0*    3         0                     152   0       0      0       0          0*    3         0                     153   0       0      1       3          0*    4         0                     154   0       0      1       0          0*    3         1                     155   0       0      4       2          0*    4         0                     156   0       0      0       0          0*    3         0                     157   0       0      0       0          0*    2         0                     158   0       0      4       4          0*    4         0                     159   0       0      0       0          0*    3         0                     __________________________________________________________________________    COM-  PUCCINIA                                                                              ERYSIPHE                                                                             PLASMOPARA                                                                            PHYTOPHTHORA                                                                            BOTRYTIS                                                                             CERCOSPORA                                                                              VENTURIA              POUND RECONDITA                                                                             GRAMINIS                                                                             VITICOLA                                                                              INFESTANS CINEREA                                                                              ARACHIDICOLA                                                                            INEQUALIS             NUMBER                                                                              (WHEAT) (BARLEY)                                                                             (VINE)  (TOMATO)  (GRAPE)                                                                              (PEANUT)  (APPLE)               __________________________________________________________________________    161   0       2      0       0         0      0         0                     162   0       2      0       0         0      0         0                     163   0       1      0       0         0      0         0                     164   0       3      0       0         0      0         0                     165   0       4      0       0         0      0         0                     166   0       0      0                 0      0         0                     167   0       3      3       3         0      2         0                     169   0       0      1       0         0      0         0                     171   0       2      0       0         0      0         0                     172   0       0      2       0         0      0         0                     173   0       0      0       0         0      0         0                     174   0       0      4       3         0      0         2                     175   0       0      4       4         0      0         0                     176   0       0      1                 0      2         0                     177   0       0      0                 0      0         0                     178   0       1      0                 0      0         0                     179   0       1      0                 0      0         0                     180   0       3      0                 0      0         0                     181   0       4      4                 0      0         0                     182   0       0      0                 0      0         0                     183   0       0      0                 0      0         0                     184   0       0      0                 0      0         0                     185   0       0      0                 0      0         0                     186   0       1      4                 0      0         0                     187   0       0      0                 0      0         0                     188   0       0      0                 0      0         0                     189   0       0      0                 0      0         0                     190   0       0      4                 0      0         0                     191   0       0      0                 0      0         0                     192   0       2      3                 0      0         0                     193   0       0      0                 0      0         0                     194   0       1      0                 0      0         2                     195   0       1      0                 0      0         3                     __________________________________________________________________________     HGHA/aji/SPEC217 & SPEC 218                                              

We claim:
 1. An amide derivative of the formula (I) ##STR21## wherein R¹is phenyl optionally substituted with halogen, lower alkyl, loweralkoxy, halo-lower alkoxy, methylenedioxy, lower alkylthio or cyano;R²is hydrogen, C₁ -C₄ alkyl or C₃ -C₅ alkenyl; X is oxygen or sulphur; R³is lower alkyl, lower haloalkyl or lower alkenyl; and E is --CN.
 2. Anamide derivative according to claim 1 whereinR¹ is phenyl optionallysubstituted in the ring with fluorine, chlorine, bromine or iodine, C₁₋₄alkyl, C₁₋₄ alkoxy, methylenedioxy, C₁₋₄ alkylthio, or C₁₋₄ haloalkyl;R² is hydrogen, C₁₋₄ alkyl or allyl; and R³ is C₁₋₄ alkyl, C₁₋₄haloalkyl or C₃₋₄ alkenyl.
 3. An amide derivative according to claim 1wherein R¹ is phenyl substituted at any of the 3-, 4- or 5-positions. 4.An amide derivative according to claim 1, wherein R² is hydrogen.
 5. Anamide derivative according to claim 1 wherein R³ is allyl or a C₁₋₄alkyl group.
 6. An amide derivative according to claim 1 wherein X isoxygen.
 7. An amide derivative according to claim 1 wherein R² ishydrogen, X is oxygen and R³ is C₁₋₄ alkyl.
 8. An amide derivativeselected from the group consisting of compounds of the formula:##STR22##
 9. An amide derivative according to claim 1 wherein R¹ ishalophenyl, R₂ is hydrogen, C₁ -C₄ alkyl or C₃ -C₅ alkenyl, E is -CN, Xis oxygen and R³ is C₁ -C₄ alkyl or C₃ -C₅ alkenyl.
 10. An amidederivative according to claim 9 and having the formula: ##STR23##
 11. Apesticidal composition comprising an effective amount of a compoundaccording to claim 9 and a pesticidally acceptable carrier therefor. 12.A pesticidal composition comprising an effective amount of a compoundaccording to claim 10 and a pesticidally acceptable carrier therefor.13. A method for combating plant fungi which comprises applying to saidfungi, to the plant, to the seed thereof or to the locus of the plant orseed an effective amount of a compound according to claim
 9. 14. Amethod for combating plant fungi which comprises applying to said fungi,to the plant, to the seed thereof or to the locus of the plant or seedan effective amount of a compound according to claim
 10. 15. Apesticidal composition comprising as an active ingredient, an effectiveamount of an amide derivative as defined in claim 1 together with acarrier or diluent.
 16. A method of inhibiting the growth of unwantedplants, which comprises applying to the plants, or to the locus thereof,a phytotoxic amount of a compound as defined in claim
 1. 17. A methodfor combating fungi which comprises applying to the fungi, or the locusthereof, a fungicidally effective amount of a compound as defined inclaim
 1. 18. A method of combating fungal disease in a plant whichcomprises applying to the plant, to the seed of the plant, or to thelocus of the plant, or seed, a compound as defined in claim 1.